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Linear and Nonlinear Optical Responses of Nitrobenzofurazan-

Sulfide Derivatives: DFT-QTAIM Investigation on Twisted
Intramolecular Charge Transfer
Balkis Abdelaziz, Imen Chérif, Bouzid Gassoumi, Salvatore Patanè, and Sahbi Ayachi*
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ABSTRACT: In this study, we report on the green fluorescence exhibited by nitro-

benzofurazan-sulfide derivatives (NBD-Si, i = 1−4). The optical responses of these studied
compounds in a polar methanol solvent were simulated by the use of time-dependent density
Downloaded via 49.37.8.255 on January 20, 2025 at 10:07:51 (UTC).

functional theory (TD-DFT) employing the Becke-3-Parameter-Lee−Yang−Parr (B3LYP)

functional along with the 6-31G(d,p) basis set. The computed energy and oscillator strength
(f) results complement the experimental results. The band gap was calculated as the difference
between the lowest unoccupied molecular orbital (LUMO) and the highest occupied
molecular orbital (HOMO). Additionally, the density of states (DOS) was computed,
providing a comprehensive understanding of the fundamental properties of these materials and
further corroborating the experimental data. When the experimental data derived from
ultraviolet/visible (UV/visible) and fluorescence spectroscopic techniques and those from
simulated spectra are analyzed, the extracted values match up adequately. In addition, the
NBD-sulfide compounds exhibit a large Stokes shift up to 85 nm in a polar methanol solvent.
They are hypothesized to represent a novel paradigm of excited-state intramolecular charge transfer (ICT). To understand the
intrinsic optical properties of NBD-Si materials, an ICT was identified, and its direction within the molecule was evaluated using the
ratio of βvect and βtotal, values extracted from the computed nonlinear optical (NLO) properties. Moreover, the reduced density
gradient (RDG)-based noncovalent interactions (NCIs) were employed to characterize the strength and type of NBD-Si
interactions. Furthermore, noncovalent interactions were identified and categorized using the Quantum Theory of Atoms in
Molecules (QTAIM) analysis. Ultimately, the combination of Hirshfeld surface analysis and DFT calculations was utilized to
enhance the characterization and rationalization of these NCIs.

1. INTRODUCTION experimental communities, with numerous applications in

Since the first report on the intramolecular charge transfer optics, optoelectronics, photonics, and nanophotonics.17,18
These NLO materials are greatly desirable due to their facile
(ICT)-based 4-(dimethylamino) benzonitrile (DMABN) mol-
synthesis and superior flexibility. This offers the opportunity to
ecule, as a groundbreaking example of electron donor/acceptor
fine-tune their structural and optoelectronic characteristics by
(D/A), by Lippert et al.,1 there have been great efforts to obtain
designing chromophores with large first hyperpolarizability
ICT-based aryl amine compounds. This has attracted
(β).19,20
considerable attention from the scientific publishing community
Methods of experimental and quantum chemistry have been
owing to their potential ability to design new nonlinear optical
widely used to evaluate the properties of NBD appended to
(NLO) systems,2 electro-optical switches,3 and organic light-
morpholine,21 piperidine,22 pyrrolidine,23 and other electro-
emitting diodes.4−6 Furthermore, they find utility solar energy
philic systems involving NBD-Cl, NBD-OCH3, and NBD-
conversion7−11 and as fluorescence sensors. However, quantify-
OC6H524
ing the extent of ICT remains a challenge for the scientific
The present work reports the predicted optical (ultraviolet−
community. First-order hyperpolarizability and therefore the visible (UV−vis) and photoluminescence (PL)) properties of
second-order NLO responses are related to an ICT within the four examples of NBD-sulfides.25 The main objective was to
molecule.12 Particularly, the investigation of π-conjugated
systems with D/A moieties at opposite ends reveals a strong
NLO response. Noncentrosymmetric D-π−A dipolar com- Received: June 27, 2023
pounds are often used to achieve first- or second-order nonlinear Revised: October 7, 2023
polarizabilities. The electron capacity of the D and the electron- Accepted: November 1, 2023
withdrawing capacity of the A groups play a key role in Published: November 16, 2023
introducing the ICT extent.13−16 The design of NLO materials
is a groundbreaking research area for both the theoretical and
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Scheme 1. Applying the SNAr Mechanism to Sulfides with an NBD-Cl Moiety to Convert Them into NBD-Si, 3a−3d,
Compounds25

Figure 1. Optimized geometric structures of investigated compounds revealing NCIs.

understand the substituent effects on optical responses, validate 2. COMPUTATIONAL DETAILS AND MODELING
the calculation method, and examine the extent of the ICT and APPROACH
NLO characteristics based on the findings. By the nucleophilic The Gaussian 09 package26 was employed to optimize the
aromatic substitution (SNAr) method, the electrophile NBD-Cl geometry of the NBD-Si (i: 1−4) molecular structures. DFT
reacted with mercaptoderivatives 2a−2d acting as nucleophilic calculations were performed in polar methanol (CH3OH) using
molecules (namely, 2a, 2-pyridinethiol; 2b, 4-pyridinethiol; 2c, the IEFPCM solvent model27 and the hybrid B3LYP func-
N-acetylcysteamine; and 2d, N-acetylcysteine), affording the tional28,29 with the 6-31g(d,p) basis set.30
thioether derivatives 3a−3d (see Scheme 1). Gauss View 5.0.831 was utilized to visualize and analyze the
The compounds will hereafter be referred to as NBD-Si (i: 1− output files. The stable molecular structure of each molecule was
4), respectively. The structure of the designed molecules (3a− next employed to extract the energy levels of HOMO (εHOMO)
3d) was supported by 1H and 13C NMR, Fourier-transform and LUMO (εLUMO), dipole moment (μ), and DOS spectrum.
infrared (FTIR), and mass spectroscopy, and their optical Therefore, the TD-DFT method32 was employed to predict the
electronic absorption spectra and the obtained results were
responses are reported.25 In this study, we employ density
subsequently compared with other DFT methods, including the
functional theory (DFT) and its time-dependent-DFT (TD- Coulomb-attenuated hybrid exchange-correlation functional
DFT) to calculate electronic characteristics, including highest (CAM-B3LYP), 33 the Tamm-Dancoff approximation
occupied molecular orbital (HOMO) and lowest unoccupied (TDA),34 and the hybrid B3PW91 exchange-correlation
molecular orbital (LUMO) energy levels, UV−visible optical functionals.35 We performed QTAIM analysis to investigate
absorption and emission spectra, dipole moment variation the noncovalent interactions (NCIs). The Multiwfn_3.7
(Δμ), average polarizability, and NLO properties. software36 has been utilized to generate the electron localization
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Table 1. Geometric Parameter Obtained in the Ground (S0) Statea

bond length (Å) dihedral angle (°)
structures L1 L2 ϕ dipole moment (μ, D) Δμ (D)
NBD-S1 1.757 (1.695) 1.807 (1.780) 2.98 (27.35) 13.005 (14.779) 1.774
NBD-S2 1.760 (1.699) 1.799 (1.776) 1.41 (27.95) 8.083 (9.191) 1.108
NBD-S3 1.747 (1.695) 1.838 (1.821) 0.035 (0.237) 12.785 (14.905) 2.120
NBD-S4 1.750 (1.697) 1.840 (1.823) 4.56 (3.37) 12.034 (13.805) 1.771
a
The values in parentheses correspond to excited (S1) state.

function (ELF), the localized orbital locator (LOL), and the electrons is characterized by LUMOs acting as electron
RDG analyses. We also used the Visual Molecular Dynamics acceptors.46 Figure 2 depicts the HOMOs and LUMOs contour
(VMD) program37 to display the iso-surfaces. The Hirshfeld graphs, with the positive phase colored red and the negative
(HS) surface was computed using the Crystal Explorer 17.5 phase colored green.
program.38 To explore the NLO NBD-Si characteristics, electric
dipole moment, polarizability (α), and static first and second
hyperpolarizabilities (β and γ) were computed in methanol
solvent.

3. RESULTS AND DISCUSSION

3.1. Geometric and Energetic Parameters. First of all,
the geometries of the NBD-Si (i: 1−4) compounds in methanol
were optimized in both their ground (GS) and excited (ES)
states employing the B3LYP and CIS39 approaches with the 6-
31g(d,p) basis set, respectively. The geometry-optimized
molecular structures are displayed in Figure 1, and the selected
geometrical parameters, including bond lengths and dihedral
angles, are listed in Table 1.
According to structural data, the optimized structures are
found to mostly contain three forms of noncovalent contacts,
namely, N---H, O---H, and N---O bond interactions, which are Figure 2. HOMO−LUMO contour plots of the studied compounds
responsible for their stability. The computed dipole moment of with gap energy.
the first excited state is also reported in Table 1. The geometrical
parameters associated with these noncovalent contacts in GS It appears that the FMOs distribution in the investigated
and ES states are illustrated in Figure 1. All of these values are compounds is almost the same. It is found that the electronic
found to be shorter than the sum of van der Waals (VdW) radii charge density distribution of HOMO is located all over the
[2.75 Å (N---H), 2.72 Å (O---H), and 3.07 Å (N--O)]. It is clear molecular structures, while the electronic charge density
that the values of these short contacts decrease upon excitation. distribution of LUMO is mainly focused on the NBD moiety.
Table 1 highlights that the variation in the dihedral angle ϕ This reveals the presence of an ICT inside the studied molecules
and the electric dipole moment are the main differences between from sulfide groups to the NBD acceptor moiety. The FMO’s
GS and ES. The value of dihedral angle ϕ, calculated between molecular characteristics-based chemical descriptors, including
the NBD moiety and the sulfide group, in the ES is larger than εHOMO, εLUMO, energy gap (Eg), ionization potential (IP),
that calculated in the GS for NBD-Si (i: 1−3). Ultimately, all of electron affinity (EA), global hardness (η), chemical potential
the optimized structures show that the title compounds involve (μ), electronegativity (χ), and electrophilicity (ω), were
twisted geometry. As shown in Table 1, the dipole moment in extracted from calculations, and results are presented in Table
each system was found to be higher in the S1 state than that in 2. The energy gap (Eg) serves as a key indicator of a molecule’s
the S0 one, increasing by 1−3 D. Additionally, we have looked at stability and chemical reactivity.47,48 According to our findings,
the bridge length variations (L1 and L2) of the investigated the energy gaps of the investigated molecules ranged from 3.255
compounds. As seen, the changes in electron delocalization in to 3.354 eV. The compounds NBD-S2 and NBD-S1 demon-
the molecular structure lead to only a small difference in bond strated the highest and lowest values, respectively. The
lengths between the GS and ES states. compound NBD-S2 is characterized by a lower reactivity and
Using the hybrid functional B3LYP in conjunction with the greater stability, indicating higher chemical hardness. On the
empirical dispersion correction D3 (B3LYP-D3), 40 the other hand, the compound NBD-S1 is identified as highly
structural parameters for all optimized molecular structures reactive, less stable, and soft. Band gap energy is recognized as a
remained unchanged (see Table S1, Supporting Information). significant factor that offers valuable information regarding the
3.2. FMOs and Quantum Theoretical Parameters. The photovoltaic efficiency of materials used in photovoltaic
frontier molecular orbitals (FMOs), formed mainly by the applications.49,50
HOMO/LUMO iso-surfaces, are the significant orbitals in a Additionally, the neutral, cation, and anion-optimized
molecule. The FMOs play an important role in judging optical structures are used to compute EA and IP, which elucidate the
and electrical performance, in addition to their chemical barrier injection energies of holes and electrons. The readings of
properties.41−45 The ability to donate electrons is qualified by EA and IP are, respectively, in the ranges of 3.66−3.74 and
HOMOs acting as electron donors, and the aptitude to accept 6.34−6.56 eV. The best electron donor is the molecule NBD-S1,
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Table 2. Calculated Electronic Parameters and Derived Quantum Chemical Parameters for the Investigated Molecules (EF
Represents the Fermi Energy)
energy levels chemical reactivity descriptors
compounds εHOMO (eV) εLUMO (eV) EF (eV) Eg (eV) μ (eV) η (eV) ω (eV) χ = −μ (eV) IP (eV) EA (eV)
NBD-S1 −6.615 −3.359 −4.987 3.255 −4.987 1.628 7.638 4.987 6.343 3.679
NBD-S2 −6.742 −3.388 −5.065 3.354 −5.065 1.677 7.648 5.065 6.574 3.745
NBD-S3 −6.607 −3.332 −4.969 3.275 −4.969 1.637 7.540 4.969 6.473 3.511
NBD-S4 −6.638 −3.345 −4.991 3.293 −4.991 1.646 7.566 4.991 6.500 3.530

which has the lowest ionization value (IP = 6.342 eV). Although Table 3. Vertical Wavelength (λ, nm) and the Oscillator
the best electron acceptor is NBD-S2, which has the highest Strengths (f) Contributing to S0 → S1 Electronic Transitions
affinity (EA = 3.744 eV). Moreover, using εHOMO and εLUMO, for Investigated Molecules, Computed by the TD-B3LYP/6-
chemical potential (μ), global hardness (η), and electro- 31g(d,p) Method in Methanol Solvent
negativity (χ) can be determined as follows:
1 1 λabs,exp
max major
= 2 ( HOMO + LUMO); = 2 ( LUMO HOMO); χ = −μ. compounds (nm) f max contribs (%) minor contribs (%)
51,52 H−5→L H → L + 4 (3%)
Besides this, the electrophilicity (ω) has been computed NBD-S1 271 0.0095
2 (94%)
using both chemical potential and global hardness ( = 2 ). A 306 0.1295 H→L+1
(96%)
molecule with a low electrophilicity is regarded as a strong 426 0.3622 H → L (98%)
nucleophile, whereas a molecule with a high electrophilicity is λabs,exp
max = 407 nm25
regarded as a strong electrophile. The results indicate that NBD- NBD-S2 265 0.0549 H−6→L H → L + 4 (6%)
S1 is a good nucleophile since it has lower values of (ω), whereas (88%)
NBD-S4 is a good electrophile. 300 0.1246 H→L+1
(96%)
Among the electronic properties of the materials under study,
409 0.3611 H → L (98%)
εHOMO and εLUMO are particularly crucial, as they facilitate the
λabs,exp = 400 nm25
calculation of both Eg and EF energies. The obtained values are max
NBD-S3 265 0.0464 H−5→L H − 1 → L + 1 (8%),
listed in Table 2. The B3LYP-D3/6-31g(d,p) level of theory was (81%) H → L + 2 (7%)
also applied to extract electronic parameters for the investigated 304 0.1288 H→L+1
molecules (see Table S2, Supporting Information). As shown in (97%)
Table S2, no appreciable changes have been detected. 415 0.3635 H → L (98%)
3.3. Electronic Spectra Analysis of the Investigated λabs,exp
max = 414 nm25
NBD-Si Molecules. The optical absorption (UV−vis) and the NBD-S4 265 0.0474 H−6→L H → L + 3 (6%)
emission properties of NBD-Si molecules, in methanol, are given (86%)
305 0.128 H→L+1
in Tables 3 and 4, respectively, while their related electronic (97%)
spectra are shown in Figure 3. The most intense absorption 415 0.3733 H → L (98%)
appears at 409−415 nm. A bathochromic shift of the absorption λabs,exp = 411 nm25
max
maxima is evident after functionalization with suitable sulfide
groups, such as 2-pyridinethiol. In all cases, the maxima originate
from HOMO−LUMO electronic transitions, with significant electron donor and the nitro electron-withdrawing groups of the
contributions of 98%. Based on FMO’s distribution analysis, NBD moiety.
these electronic transitions are associated with the π → π* type. To enhance the result validation, we employed three DFT
In fluorescence spectroscopy, the difference in spectral methods (CAM-B3LYP, TDA, and B3PW91) to predict UV−
position between the first absorption band’s maximum and the vis properties for the studied molecules.
fluorescence emission’s maximum is identified as the Stokes shift The computed results were compared with the available
(SS), which can be expressed in wavelength: SS = λmax max
PL λabs . In experimental data (see Table S3, Supporting Information).
some cases, significant reabsorption effects due to the overlap of Overall, we consider that the TD-B3LYP/6-31g(d,p) level of
absorption and emission spectra limit practical applications. To theory can be proposed to obtain better results at a reasonable
address this, the development of D−A or D-π−A push−pull cost.
systems aims to minimize the overlap between absorption and 3.4. DOS Analysis. Nearby orbitals within the boundary area
emission spectra, effectively reducing reabsorption losses.53,54 may have quasi-degenerate energy levels, so it may not be
Herein, NBD-sulfide compounds exhibit a large SS up to 85 nm practical to use only HOMO and LUMO to define the FMOs.57
in polar methanol solvent (see Figure 3). The ICT phenomenon Therefore, the DOS spectra for the investigated compounds
is an alternative reason for the large SS. In summary, the were generated by the Gauss Sum 3.0 software (the full width at
extracted values from the experimental data obtained through half-maximum (fwhm) is 0.3 eV).58 Figure 4 shows the obtained
UV/visible and fluorescence spectroscopic techniques (Tables 3 DOS spectra.
and 4) align well with the values derived from simulated spectra. Virtual orbitals, also known as acceptor orbitals, are
Furthermore, the change in dipole moment relaxes the polar unoccupied, while filled orbitals are termed donor orbitals.
solvent around the excited molecule, leading to the lowest The DOS exhibits a positive value when indicating bonding
energy state.55 This is supported by assignments previously interactions, a negative value for antibonding interactions, and
reported by Heberer et al.56 for NBD derivatives, where the zero when there are no bonding interactions present.59,60
lower energy band is attributed to an ICT between the sulfide Furthermore, the DOS spectra directly provide the energy gap.
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Table 4. Vertical Wavelength (λ, nm) and the Oscillator kinetic energy density. Furthermore, ELF is rooted in the
Strengths ( f) Contributing to S1 → S0 Electronic Transitions analysis of electron pair density, whereas LOL identifies and
of Investigated Molecules, Calculated by the TD-B3LYP/6- characterizes the gradients of localized orbitals.66 The ELF and
31g(d,p) Method in Methanol Solvent. The excitation LOL color-filled maps generated by Multiwfn software for the S0
wavelengths varied from 366 to 380 nm and S1 states of the investigated materials are shown in Figures 6
and 7, respectively. These maps range from 0 to 1. An ELF value
λPL,exp
max major contribs
compounds (nm) f max (%) minor contribs (%) greater than 0.5 corresponds to the area in which the bonding
and nonbonding electrons are localized, whereas a value under
NBD-S1 292 0.1476 L → H − 4 (54%), L + 4 → H (8%)
L→H−2 0.5 indicates a delocalized electronic region.67 LOL values
(23%) exceed 0.5 in areas where the electron density is controlled by
366 0.0646 L + 1 → H (80%) L + 1 → H − 1 (13%) electron localization. Several colors are shown in the ELF and
515 0.5543 L → H (88%) L → H − 1 (8%) LOL maps. High ELF or LOL values are visually represented by
25
λPL,exp
max = 522 nm the red color, indicating the presence of localized electrons
NBD-S2 287 0.0226 L+2→H−3 L → H − 4 (3%), surrounding hydrogen atoms. The delocalized electron cloud
(79%) L + 10 → H − 3
(8%) surrounding C, N, S, and O atoms is visually represented by the
366 0.0625 L + 1 → H (90%) L + 1 → H − 2 (4%) blue. From the LOL maps, it is evident that the central region of
513 0.5486 L → H (95%) the hydrogen atom appears white, indicating an electron density
λPL,exp
max = 521 nm
25 that surpasses the upper limit of the color scale (0.8). In
NBD-S3 290 0.1458 L → H − 3 (73%) L + 3 → H (12%) addition, the red regions between C−C, C−N, C−S, and N−O
L → H − 4 (8%) atoms present covalent interactions with a high LOL value.
367 0.059 H → L + 1 (95%) 3.7. MEP Analysis. The molecular electrostatic potential
507 0.5614 L → H (97%) (MEP) describes the charge distribution around the molecular
25
λPL,exp
max = 516 nm structure generated by its nuclei and electrons. The distribution
NBD-S4 291 0.1482 L → H − 3 (73%), L + 4 → H (12%), of charge can be used to determine how molecules interact with
L → H − 5 (5%), each other.68,69 It also serves as a tool for identifying reactive
L → H − 4 (3%)
365 0.0558 L + 1 → H (95%)
sites for nucleophilic and electrophilic reactions.70 The
503 0.5636 L → H (97%)
nucleophilic sites assume a high attraction, while the electro-
λPL,exp 25 philic sites show a high repulsion. The MEP 3D plots of all
max = 542 nm
structures in both S0 and S1 states were computed by employing
the B3LYP/6-31(d,p) level, as illustrated in Figure 8. The figure
3.5. RDG Analysis. The molecular stability can be attributed presents the electrostatic potential values in false colors,
to the presence of relatively weak intra- and intermolecular progressing in order: red < orange < yellow < green < blue.
interactions that can be identified and studied by the NCI The positive (blue) areas of the MEP are the preferred
methodology. This method uses RDG to provide further nucleophilic attack sites, whereas the negative (red-yellow)
evidence for NCIs. The RDG is a fundamental dimensionless areas are the preferred electrophilic attack sites, and green colors
parameter based on the relationship between the electron are neutral regions. As shown in the MEP three-dimensional
density (ρ) and its derivative,61,62 expressed as (3D) graphs, areas with negative potential are over the
1 | | electronegative atoms (nitrogen and oxygen atoms) of NBD
RDG (r) = 2 1/3 4/3 moieties and the sulfide groups, which support electrophilic
2(3 ) (1) attacks.
The result of the product of the electron density ρ(r) and the The positive potential zones are over the hydrogen atoms,
sign of the second-lowest eigenvalues of the electron density favoring nucleophilic attack. For all studied molecules, the NBD
Hessian matrix (λ2(r)) is highly significant in anticipating the moieties are very evident in the red-yellow region, confirming
nature of interaction. The attractive, repulsive, and intermediate the acceptor properties of this group. Consequently, the
interactions correspond to sign(λ2) × ρ < 0 and sign(λ2) × ρ > 0 presence of electrophile and nucleophilic attacks in these
and sign(λ2) × ρ ≈ 0.63 Two-dimensional (2D) scatter plots and molecules supports their push−pull (D−A) nature.
the 3D-RDG isosurface densities of studied molecules in the GS 3.8. QTAIM Analysis. The QTAIM analysis, developed by
are indicated in Figure 5. Correspondingly, as shown in the RDG Bader and co-workers,71 identifies the nature and type of intra-
plots, there are three kinds of spikes in the zone between −0.05 and intermolecular H-bonds, including NCIs,72 in a topological
and 0.05 a.u. The blue regions represent attractive interactions manner. According to QTAIM theory, the bond path (BP) is the
like H-bonds, the red regions signify repulsive interactions, such link between an interacting atom and the saddle point where the
as steric effects, and the green regions take place for very weak gradient of the electron density is zero, also called the critical
interactions, typically VdW ones.64 Looking at the NCI-RDG point (CP). The QTAIM graphs are obtained using Multiwfn
graphs, the van der Waals interactions are clearly shown within software and are illustrated in Figure 9. As shown in the graph,
our NBD molecules. As well, the detection of a blue surface three types of critical points can be identified: a large red spot
highlights the existence of H-bond interactions. Moreover, red (+3,−3) represents the nuclear critical point (NCP), a small
areas are positioned in the center of the rings, demonstrating the orange spot (+3,−1) indicates the bond critical point (BCP),
effect of steric repulsion. and a yellow spot (+3,+1) is the ring critical point (RCP). The
3.6. ELF and LOL Topological Analyses. ELF and LOL BCPs offer an effective measure of the distance between atoms
analyses, developed and explained by Silvi and Sain,65 both in a molecular system.73−75 Mainly, hydrogen bond interactions
conduct covalent bonds analysis, revealing areas in the can be efficiently characterized and quantified by the use of a
molecular space with high electron pairing potential. ELF and variety of topological parameters: electron density ρ (r) and its
LOL have comparable chemical maps since they depend on the Laplacian ∇2ρ (r), kinetic energy G (r), potential energy V (r),
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Figure 3. Electronic spectra (UV−vis and PL) achieved at the TD-B3LYP/6-31g(d,p) level of theory of materials.

Figure 4. DOS spectra obtained at the B3LYP/6-31g(d,p) level, labeled as (a−d), corresponding to NBD-Si (i = 1−4).

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Figure 5. RDG scatter plots (left) and NCI plots (right) of the investigated materials in GS.

Figure 6. Color-filled map of the ELF (top) and LOL (bottom) of studied molecules in their S0 states.

kinetic energy of Hamiltonian H (r) = G (r) + V (r), and the First, when ∇2ρ (r) > 0 and H (r) > 0, it denotes weak H-bonds.
binding energy BE, calculated by means of the expression Second, when ∇2ρ (r) > 0 and H (r) < 0, it signifies moderate H-
provided by Espinosa et al.:76 BE = V (r)/2. Among them, the bonds. Lastly, when ∇2ρ (r) < 0 and H (r) < 0, it indicates the
most significant are the electron density ρ (r) and its Laplacian strongest H-bonds.
∇2ρ (r), which are used to identify the nature of the bond or Table 5 presents the topological parameter values at the CBs
interaction. A large ρ (r), greater than 0.20 a.u. and negative ∇2ρ of various NCI examples. In the QTAIM molecular graphs,
(r) values show a covalent bond, whereas small ρ (r), less than NBD-S1 exhibits two BCPs representing N−O and N−H
0.10 a.u. and negative ∇2ρ (r) values signify a closed-shell interactions, while NBD-S2 has a single N−O interaction. NBD-
interaction (ionic, H-bond, VdW). In Figure 9, solid lines S3, in comparison to NBD-S1, features both N−H and N−O
indicate CBs, while NCIs are shown as dashed lines. Specifically, interactions. Alternatively, there are four kinds of interactions
H-bond interactions can be classified into three categories.77 obtained in the last compound: O−H, N−H, N−O, and C−H
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Figure 7. Color-filled map of (top) and LOL (bottom) of the studied molecules in their S1 states.

Figure 8. MEP 3D plots of studied molecules.

Figure 9. QTAIM molecular graphics with examples of BCPs for the investigated molecules.

interactions. The ρ(r) values of bond critical points vary from Popelier.78 Also, the positive values of the energy density H (r)
0.0079 au to 0.012 a.u., and their Laplacians range from 0.030 to justify the weak H-bond. In addition, the band energy appears
0.050 a.u., which are similar to the values offered by Koch and between −5.382 and −12.602 kJ/mol. The N−H and O−H
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Table 5. Topological Parameters Computed for Investigated Compounds at BCPs

compound interaction ρ (r) ∇2ρ (r) G (r) V (r) H (r) BE (kJ/mol)
NBD-S1 1 0.010 0.036 0.0075 −0,0058 0.0016 −7.613
2 0.012 0.050 0.0110 −0.0095 0.0015 −12.471
NBD-S2 1 0.012 0.050 0.0110 −0.0095 0.0015 −12.471
NBD-S3 1 0.010 0.038 0.0077 −0.0059 0.0018 −7.745
2 0.012 0.050 0.0110 −0.0096 0.0014 −12.602
NBD-S4 1 0.0079 0.031 0.00603 −0.0041 0.0019 −5.382
2 0.0083 0.030 0.0065 −0.0053 0.0012 −6.957
3 0.010 0.038 0.0078 −0.0059 0.0018 −7.745
4 0.012 0.049 0.0110 −0.0096 0.0014 −12.602

interactions in NBD-S 3 and NBD-S 4 , respectively, are interactions of the investigated compounds were dominated by
considered the strongest ones, with BE = 12.602 kJ/mol. H···O/O···H, H···H, C···N/N···C, C···H/H···C, O···O, and C···
3.9. Hirshfeld Surface (HS) Analysis. The analysis of the O/O···C. The major contribution of Hirschfeld’s total surface in
Hirshfeld surface (HS)79−81 offers insights into the character- all compounds is attributed to H···O/O···H interactions with
istics of molecular surfaces and introduces a novel method to 28.9, 26.1, 23.9, and 31.4% for NBD-S1, NBD-S2, NBD-S3, and
visualize intermolecular interactions. HS analysis is utilized to NBD-S4, respectively. These interactions are characterized by
examine intermolecular interactions involved in the stabilization one large spike in the middle of the scattered points. The
of crystal packing for the studied compounds.82,83 This interactions with the second contribution, however, vary
visualization is achieved through color coding, which distin- depending on the molecule. NBD-S1 and NBD-S2 exhibit
guishes short- or long-term contacts.84 HS may be mapped with interactions such as H···H, C···N/N···C, C···O/O···C, and C···
various properties, such as dnorm, curvedness, and shape index. C. On the other hand, NBD-S3 and NBD-S4 involve interactions
Figure 10(i−iii) displays the molecular HS (dnorm, curvedness, such as C···O/O···C, C···H/H···C, O···O, and H···H. The
and shape index) of the studied molecules. The Hirshfeld analysis of Hirshfeld surfaces also indicates the existence of
molecular surfaces are produced using a standard (high) surface additional weak intermolecular interactions that make modest
resolution. In the case of NBD-S1, the 3D dnorm surfaces are contributions to the surface area (C···S/S···C, N···O/O···N. and
mapped on a fixed color scale ranging from −1.1876 Å (red) to H···/S···H).
5.9755 Å (blue). For NBD-S2, the mapping ranges from 3.10. NLO Responses for Investigated Compounds.
−1.1858 Å (red) to 6.038 Å (blue). Similarly, for NBD-S3, the Polarizability and hyperpolarizability measurements can be used
range is from −1.2575 Å (red) to 6.4383 Å (blue), and for NBD- to explore the NLO characteristics of the investigated molecules.
S4, it is from −1.2364 Å (red) to 5.8931 Å (blue). Curvedness is The significance of these two parameters was crucial for defining
mapped within the range of −4.0 to 4.0, while the shape index is ICT properties.88,89 By means of the B3LYP/6-31g(d,p) level of
mapped in the color range of −1.0 to 1.0. The dnorm attributed is theory, we evaluated the static dipole moment (μ), mean
a symmetric function that evaluates the surface distances (di and polarizability (α0), polarizability anisotropy (Δα), and static first
de) between nuclei inside and outside the HS area, respectively, and second hyperpolarizabilities (β and γ) of the investigated
in relation to their respective van der Waals (vdW) radii. The red molecules. The relevant expressions used for the calculation are
and blue regions, corresponding to the negative and positive as given below90−93
dnorm values, display shorter and longer contacts, respectively. 2 2 2
However, the white color designates the contacts around the tot
= ( x
+ y
+ z
) (2)
VdW radii (dnorm values near zero). On the dnorm surface, the
deep red spots indicate intermediate contacts involved in H- ( xx + yy + zz)
bonds.85 The red spots in Figure 10(i) are assigned to N−H···S, 0 =
(3)
3
N−H···O, and C−H···O hydrogen bonds for compounds NBD-
S1 and NBD-S2, C−H···S, C−H···N, N−H···O, and C−H···O 1 2 2 2
H-bonds for compounds NBD-S3 and NBD-S4. Additionally, the = [( xx yy) +( yy zz) +( zz xx)
2
presence of red/blue triangles and the expansive green region in 2 2 2 1/2
the curvedness triangles within the shape index serve as + 6( xy + yz + zx )]
indicators of C−H···π and π···π stacking interactions taking (4)
place among the molecules. 2 2 2 1/2
The 2D depiction of the HS is commonly referred to as a 0 =( x + y + z ) (5)
fingerprint,86 as it has the ability to unveil additional insights into
the intermolecular contacts. The 2D fingerprint plots can be And,
decomposed to highlight the interactions and the area = + +
corresponding to each of these interactions. The HS surfaces x xxx xyy xzz

and the 2D fingerprint plots have been generated using the = + +

y yyy xxy yzz
Crystal Explorer program.87 The decomposed 2D fingerprint
plots of all compounds and all major and minor intermolecular z = zzz + zyy + xxz
interactions with the percentage of contributions are shown in
Figure 10(iv). In this study, the 2D fingerprint plots show 1
0 = [( xxxx + yyyy + zzzz) + 2( xxyy + yyzz + zzxx )]
various types of interactions that ensure the structure’s cohesion. 5
The overall 2D fingerprint plot showed that the intermolecular (6)

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Figure 10. continued

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Figure 10. Hirshfeld surfaces mapped over (i) dnorm, (ii) shape index, (iii) curvedness, and (iv) percentage contributions of the various intermolecular
contacts and 2-D fingerprint plots of each studied compound.

where αxx, αyy, and αzz are the polarizability tensor components, respectively. The calculated values are given in Table 6. These
and βxxx, βxyy, βxzz, βxxy, βyyy, βyzz, βxxz, βzyy, βzzz and γxxxx, γyyyy, γzzzz, values have been converted into electrostatic units (for α, 1 a.u. =
γxxyy, γyyzz, and γzzxx are the first- and second-order hyper- 0.1482 × 10−24 esu; for β, 1 a.u. = 8.6391 × 10−33 esu and for γ, 1
polarizability tensor components along the x, y, and z axes, a.u. = 0.000504 × 10−36 esu).
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Table 6. Computed Electric Dipole Moment (μ), Polarizability (α), 1st- and 2nd-Order Hyperpolarizability (β) and (γ),
Respectively, for the Studied Compounds
polarizability, α × 10−24 esu 2nd-order hyperpolarizability, γ × 10−36 esu
NBD-S1 NBD-S2 NBD-S3 NBD-S4 NBD-S1 NBD-S2 NBD-S3 NBD-S4
αXX 40.949 39.721 36.733 40.046 γXXXX 43.838 26.617 23.898 25.751
αYX −2.097 −0.311 0.951 1.826 γXXYX −0.994 −0.243 2.322 5.444
αYY 17.352 20.334 17.230 19.470 γXXYY 0.533 1. 497 1.619 3.658
αZX 7.718 6.817 40.661 3.9125 γYXYY −0.627 −0.118 0.316 2.089
αZY 3.148 0.532 0.438 −1.159 γYYYY 1.725 2.974 1.530 2.927
αZZ 52.684 48.045 52.402 55.105 γXXZX 34.132 11.633 10.861 8.619
α0 = αISO 36.995 36.034 35.455 38.207 γXXZY −1.043 −0.179 1.844 2.542
Δα = αANISO 34.541 27.333 31.375 31.936 γYXZY −0.465 0.699 0.730 1.281
1st-order hyperpolarizability, β × 10−30 esu γYYZY 0.806 0.177 0.098 0.368
βXXX −1.230 −0.455 0.267 −0.040 γXXZZ 42.439 8.534 7.033 5.798
βXXY −0.152 −0.035 0.206 0.462 γYXZZ −2.468 −0.589 2.572 4.280
βYXY −0.126 0.045 −0.991 −0.551 γYYZZ −1.362 −1.004 −0.617 1.866
βYYY −0.350 −0.014 0.611 −0.315 γZXZZ 111.977 49.662 42.508 42.218
βXXZ −2.379 −2.923 −1.778 −1.865 γZYZZ −5.407 −2.173 5.666 5.970
βYXZ −0.339 −0.072 0.207 0.560 γZZZZ 520.226 382.615 365.442 391.169
βYYZ −0.882 −0.622 −1.307 −0.909 γ0 = γ|| 129.800 86.051 81.387 88.497
βZXZ 7.168 3.798 3.628 3.559 γ⊥ 43.267 28.684 27.129 29.500
βZYZ −0.853 −0.346 0.639 1.217 electric dipole moment (debye)
βZZZ 87.016 74.188 79.671 79.848 μx 8.396 −4.646 −7.934 −6.592
|| (Z) 50.252 42.386 45.951 46.245 μy 1.798 −0.004 4.362 2.787
⊥ (Z) 16.750 14.129 15.317 15.415 μz 9.767 −6.615 −9.027 −9.674
|βvect| 66.466 59.752 75.647 63.268 μtot 13.005 8.084 12.785 12.034
β0 83.967 70.725 76.654 77.143
|βvect|/β0 0.791 0.844 0.722 0.820 βvec = ∑iβiμi/μ [i = x,y,z]100
θ (deg) 37.74 32.45 43.80 34.93

The calculated electric dipole moments are found to be from the βZXZ tensor component. Furthermore, based on the
13.005, 8.084, 12.784, and 12.034 D for NBD-S1, NBD-S2, collective results presented in Tables 1 and 2, it is evident that
NBD-S3, and NBD-S4, respectively. It is noteworthy that the compounds with a narrow energy gap and a lower difference in
greatest dipole moment value is observed for compound NBD- dipole moment between the S0−S1 states (Δμ) will exhibit
S1. The static polarizability (α0), values of the investigated higher first-order hyperpolarizability.
molecules increase in the subsequent order NBD-S3 < NBD-S2 < Conversely, the relationship between βvect and βtotal is
NBD-S1 < NBD-S4. Similarly, we can see that the anisotropy of acknowledged to provide significant information regarding the
polarizability (αaniso) increases in the order: NBD-S2 < NBD-S3 direction of the ICT, as the following relationship holds:
vec
< NBD-S4 < NBD-S1. The hyperpolarizability is a key property = cos( ),100 where θ characterizes the orientation between
of the NLO response, with β0 ranging from 70.725 × 10−30 to 0

83.967 × 10−30 esu. Additionally, it is noteworthy that the NBD- the vector formed by the components of βvec and the dipole
vec
S1 compound exhibits the highest values for both first- and moment vector. Note that a ratio approaching unity means
0
second-order hyperpolarizabilities, whereas the NBD-S2 com-
maximum charge delocalization.101 This phenomenon occurs
pound shows the lowest values in this regard. Notably, the first
due to the dominance of one of the first hyperpolarizability
hyperpolarizability demonstrates a direct correlation with linear
components, which significantly contributes to the overall first
polarizability values and an inverse correlation with energy gap
hyperpolarizability. As a result, a unidirectional alignment
values.94−97 In this context, there is a strong correspondence
parallel to the molecular dipole moment of ICT takes place.
between the βtot values and the observed patterns in Eg values,
Here, the calculated angle θ is in the range of 32 to 44°. This
with the compound having the smallest band gap (3.255 eV)
confirms the twisted ICT in all of the investigated NBD-Si
demonstrating the highest βtot value (83.967 × 10−30 esu).
molecules.
In this section, urea was chosen as a reference because there
was no experimental standard for the NLO properties of the
molecules of interest (μurea = 1.3732 D, αurea = 5.0477 × 10−24 4. CONCLUSIONS
esu, βurea = 372.8 × 10−33 esu, and γurea = 48 × 10−36 esu).98,99 In this study, we used the TD-B3LYP/6-31g(d,p) level of theory
The first-order hyperpolarizability of all investigated compounds to explain and predict the optical responses of four examples of
is significantly greater (i.e., ≥70 times) than that of the standard NBD derivatives in a polar methanol solvent. The studied
urea, and NBD-S1 exhibits the best NLO characteristics. These compounds, labeled NBD-Si (i = 1−4), consist of NBD and
results thus confirm that the studied molecules possess good sulfide moieties. These molecules absorb within the wavelength
NLO parameters and may be a good candidate for applications range of 250−500 nm and all emit green fluorescence in the
in optical devices. 503−515 nm range. They also exhibited large Stokes shifts, up to
According to Table 6, βtot mainly depends on the βZZZ tensor 500 meV, in polar methanol solvent. We concluded that DFT
component, while also showing supplementary contributions and its time-dependent extension (TD-DFT) can predict the
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The Journal of Physical Chemistry A pubs.acs.org/JPCA Article

optical properties of the studied molecules. Additionally, we Notes

demonstrate that the optical properties of these investigated The authors declare no competing financial interest.
systems can be systematically tuned through the choice of
substituents; including their nature, extended conjugated
systems, and strength.
■ ACKNOWLEDGMENTS
This work was realized in the frame of the Program ERASMUS+
Findings from QTAIM, ELF, and RDG analyses indicate that
KA107, FSE 2014/2020 P.O.R. Sicilia Project No. 2020-1-IT02-
the bonding between sulfide and NBD moieties is of
KA107-078488, CUP J49J21003660006. The authors also
electrostatic or hydrogen bond type. The DFT approach is
extend their sincere appreciation to the Ministry of Higher
also reliable for determining the NLO properties of the NBD-Si
Education and Scientific Research in Tunisia for the technical
compounds.
and financial support provided for this study, based on an
In our NLO analysis, we found that small nonplanar NBD-Si
agreement between the Ministry of Higher Education and
molecules with intramolecular charge transfer (ICT) character-
Scientific Research in Tunisia and the American Chemical
istics are excellent candidates for designing NLO materials.
Society (ACS).
Specifically, dipole moment (μ), polarizability (α), and first-
order hyperpolarizability (β) were larger in the case of NBD-S1
(μtot = 13.005 D, α0 = 36.995 × 10−24 esu, and β0 = 83.967 ×
10−30 esu). The twisted intramolecular charge transfer (TICT)
■ REFERENCES
(1) Lippert, E.; Lüder, W.; Moll, F.; Nägele, W.; Boos, H.; Prigge, H.;
from the sulfide to the respective NBD was clearly elucidated in Seibold-Blankenstein, I. Umwandlung von Elektronenanregungsener-
our NLO studies. Ultimately, we conducted Hirshfeld surface gie. Angew. Chem. 1961, 73, 695−706.
analysis and employed some topological approaches based on (2) Grabowski, Z. R.; Rotkiewicz, K.; Rettig, W. Structural Changes
Accompanying Intramolecular Electron Transfer: Focus on Twisted
DFT, including NCI plots and QTAIM analysis, to further Intramolecular Charge-Transfer States and Structures. Chem. Rev.
characterize and describe the NCIs. 2003, 103, 3899−4031.

■ ASSOCIATED CONTENT
* Supporting Information
sı
(3) Zhang, S. Y.; Shu, X.; Zeng, Y.; Liu, Q. Y.; Du, Z. Y.; He, C. T.;
Zhang, W. X.; Chen, X. M. Molecule-based nonlinear optical switch
with highly tunable on-off temperature using a dual solid solution
approach. Nat. Commun. 2020, 11, No. 2752.
The Supporting Information is available free of charge at (4) Kaino, T.; Tomaru, S. Organic materials for nonlinear optics. Adv.
https://pubs.acs.org/doi/10.1021/acs.jpca.3c04277. Mater. 1993, 5, 172−178.
Geometric parameters at the ground (S0) state for (5) Ong, B. S.; Wu, Y.; Liu, P.; Gardner, S. High-performance
semiconducting polythiophenes for organic thin-film transistors. J. Am.
investigated compounds obtained with B3LYP-D3/6-
Chem. Soc. 2004, 126, 3378−3379.
31g(d,p) level of theory (Table S1); computed electronic (6) Dalton, L. R.; Sullivan, P. A.; Bale, D. H. Electric field poled
parameters for investigated molecules at the B3LYP-D3/ organic electro-optic materials: state of the art and future prospects.
6-31g(d,p) level of theory, recorded in methanol solvent Chem. Rev. 2010, 110, 25−55.
(Table S2), and selected DFT methods for calculation of (7) Georgieva, I.; Aquino, A. J.; Plasser, F.; Trendafilova, N.; Köhn, A.;
vertical wavelength maxima (λ, nm) and their corre- Lischka, H. Intramolecular Charge-Transfer Excited-State Processes in
sponding oscillator strengths (f) contributing to HOMO 4-(N,N-Dimethylamino)benzonitrile: The Role of Twisting and the
→ LUMO electronic transitions for investigated mole- πσ* State. J. Phys. Chem. A 2015, 119 (24), 6232−6243.
cules in methanol solvent (Table S3) (PDF) (8) Kochman, M. A.; Durbeej, B.; Kubas, A. Simulation and Analysis
of the Transient Absorption Spectrum of 4-(N,N-Dimethylamino)-

■ AUTHOR INFORMATION
Corresponding Author
benzonitrile (DMABN) in Acetonitrile. J. Phys. Chem. A 2021, 125
(39), 8635−8648.
(9) Sissa, C.; Calabrese, V.; Cavazzini, M.; Grisanti, L.; Terenziani, F.;
Quici, S.; Painelli, A. Tuning the Nature of the Fluorescent State: A
Sahbi Ayachi − Laboratory of Physico-Chemistry of Materials Substituted Polycondensed Dye as a Case Study. Chem. - Eur. J. 2013,
(LR01ES19), Faculty of Sciences, University of Monastir, 19 (3), 924−935.
5019 Monastir, Tunisia; Email: [email protected] (10) Henson, Z. B.; Müllen, K.; Bazan, G. C. Design strategies for
organic semiconductors beyond the molecular formula. Nat. Chem.
Authors 2012, 4 (9), 699−704.
Balkis Abdelaziz − Laboratory of Physico-Chemistry of (11) Li, Y.; Wei, Q.; Cao, L.; Fries, F.; Cucchi, M.; Wu, Z.; Scholz, R.;
Materials (LR01ES19), Faculty of Sciences, University of Lenk, S.; Voit, B.; Ge, Z.; Reineke, S. Organic Light-Emitting Diodes
Monastir, 5019 Monastir, Tunisia; Department of Based on Conjugation-Induced Thermally Activated Delayed Fluo-
Mathematical and Computer Sciences, Physical Sciences and rescence Polymers: Interplay Between Intra- and Intermolecular
Charge Transfer States. Front. Chem. 2019, 7, No. 688.
Earth Sciences, University of Messina, I-98166 Messina, Italy (12) Janjua, M. R. S. A. Nonlinear optical response of a series of small
Imen Chérif − Laboratory of Physico-Chemistry of Materials molecules: quantum modification of π-spacer and acceptor. J. Iran.
(LR01ES19), Faculty of Sciences, University of Monastir, Chem. Soc. 2017, 14 (9), 2041−2054.
5019 Monastir, Tunisia (13) Belyaev, A.; Cheng, Y. H.; Liu, Z. Y.; Karttunen, A. J.; Chou, P. T.;
Bouzid Gassoumi − Laboratoire Interfaces et Matériaux Koshevoy, I. O. Acceptor Phosphonium Fluorophores. Angew. Chem.,
Avancés (LIMA), Faculté des Sciences, Université de Monastir, Int. Ed. 2019, 58 (38), 13456−13465.
5019 Monastir, Tunisia (14) Chung, H. Y.; Oh, J.; Park, J.-H.; Cho, I.; Yoon, W. S.; Kwon, J. E.;
Salvatore Patanè − Department of Mathematical and Kim, D.; Park, S. Y. Spectroscopic Studies on Intramolecular Charge-
Computer Sciences, Physical Sciences and Earth Sciences, Transfer Characteristics in Small-Molecule Organic Solar Cell Donors:
University of Messina, I-98166 Messina, Italy A Case Study on ADA and DAD Triad Donors. J. Phys. Chem. C 2020,
124 (34), 18502−18512.
Complete contact information is available at: (15) Rout, Y.; Montanari, C.; Pasciucco, E.; Misra, R.; Carlotti, B.
https://pubs.acs.org/10.1021/acs.jpca.3c04277 Tuning the Fluorescence and the Intramolecular Charge Transfer of

9907 https://doi.org/10.1021/acs.jpca.3c04277
J. Phys. Chem. A 2023, 127, 9895−9910
The Journal of Physical Chemistry A pubs.acs.org/JPCA Article

Phenothiazine Dipolar and Quadrupolar Derivatives by Oxygen (33) Yanai, T.; Tew, D. P.; Handy, N. C. A new hybrid exchange−
Functionalization. J. Am. Chem. Soc. 2021, 143 (26), 9933−9943. correlation functional using the Coulomb-attenuating method (CAM-
(16) Yadav, I. S.; Jang, Y.; Rout, Y.; Thomas, M. B.; Misra, R.; D’Souza, B3LYP). Chem. Phys. Rev. Lett. 2004, 393 (1−3), 51−57.
F. Near-IR Intramolecular Charge Transfer in Strongly Interacting (34) Hirata, S.; Head-Gordon, M. Time-dependent density functional
Diphenothiazene-TCBD and Diphenothiazene-DCNQ Push-Pull theory within the Tamm−Dancoff approximation. Chem. Phys. Lett.
Triads. Chem. - Eur. J. 2022, 28 (25), No. e202200348. 1999, 314, 291−299.
(17) Kaur, S.; Dhoun, S.; Depotter, G.; Kaur, P.; Clays, K.; Singh, K. (35) Govindarajan, M.; Ganasan, K.; Periandy, S.; Mohan, S. DFT
Synthesis, linear and nonlinear optical properties of thermally stable (LSDA, B3LYP and B3PW91) Comparative Vibrational Spectroscopic
ferrocene-diketopyrrolopyrrole dyads. RSC Adv. 2015, 5, 84643− Analysis of α-Acetonaphthone. Spectrochim. Acta, Part A 2010, 76, 12−
84656. 21.
(18) Mori, J.; Kaino, T. Molecular orbitals of benzoxadiazole (36) Lu, T.; Chen, F. Multiwfn: a multifunctional Wavefunction
compounds with optical nonlinearities. Phys. Lett. A 1988, 127, 259− analyzer. J. Comput. Chem. 2012, 33, 580−592.
262. (37) Humphrey, W.; Dalke, A.; Schulten, K. VMD: visual molecular
(19) Kim, T. D.; Luo, J.; Cheng, Z. J.; Shi, Z.; Hau, S.; Jang, S. H.; dynamics. J. Mol. Graphics 1996, 14, 33−38.
Zhou, X. H.; Tian, Y.; Polishak, B.; Huang, S.; et al. Jen, Binary (38) Spackman, P. R.; Turner, M. J.; McKinnon, J. J.; Wolff, S. K.;
Chromophore Systems in Nonlinear Optical Dendrimers and Polymers Grimwood, D. J.; Jayatilaka, D.; Spackman, M. A. CrystalExplorer: a
for Large Electrooptic Activities. J. Phys. Chem. C 2008, 112 (21), program for Hirshfeld surface analysis, visualization and quantitative
8091−9098. analysis of molecular crystals. J. Appl. Crystallogr. 2021, 54, 1006−1011.
(20) Cheng, Y. J.; Luo, J.; Huang, S.; Zhou, S.; Shi, Z.; Kim, T. D.; Bale, (39) Hajaji, S.; Zaier, R.; Ayachi, S. Difluorinated cyclopentadithio-
D. H.; Takahashi, S.; Yick, A.; Steier, W.; et al. Donor-Acceptor phene derivatives for green emitters in organic light-emitting diodes: A
Thiolated Polyenic Chromophores Exhibiting Large Optical Non- theoretical investigation. J. Phys. Chem. Solids 2021, 156, No. 110170.
linearity and Excellent Photostability. Chem. Mater. 2008, 20, 5047− (40) Grimme, S.; Antony, J.; Ehrlich, S.; Krieg, J. A Consistent and
5054. Accurate ab Initio Parametrization of Density Functional Dispersion
(21) Chérif, I.; Raissi, H.; Abieth, K.; Gassoumi, B.; Caccamo, M. T.; Correction (DFT-D) for the 94 Elements H-Pu. J. Chem. Phys. 2010,
Magazu, S.; Haj Said, A.; Hassen, F.; Boubaker, T.; Ayachi, S. 132, No. 154104.
Exploration of intramolecular charge transfer in para-substituted (41) Durig, J. R.; Little, T. S.; Gounev, T. K.; Gardner, J. K.; Sullivan, J.
nitrobenzofurazan: Experimental and theoretical analyses. Spectrochim. F. Infrared and Raman Spectra, Conformational Stability, Vibrational
Acta, Part A 2023, 301, No. 122939. Assignment, and ab Initio Calculations of Chloromethyl Isocyanate. J.
(22) Chérif, I.; Raissi, H.; Abieth, K.; Gassoumi, B.; Caccamo, M. T.; Mol. Struct. 1996, 375, 83−94.
Magazu, S.; Haj Said, A.; Hassen, F.; Boubaker, T.; Ayachi, S. (42) Yoosefian, M.; Ansarinik, Z.; Etminan, N. Density Functional
Computational studies on optoelectronic and nonlinear optical Theory Computational Study on Solvent Effect, Molecular Con-
properties of para-substituted nitrobenzofurazan compound. Mater. formations, Energies and Intramolecular Hydrogen BondStrength in
Today Commun. 2023, 35, No. 106133. Different Possible Nano-Conformers of Acetaminophen. J. Mol. Liq.
(23) Chérif, I.; Raissi, H.; Abieth, K.; Gassoumi, B.; Caccamo, M. T.; 2016, 213, 115−121.
Magazu, S.; Haj Said, A.; Hassen, F.; Boubaker, T.; Ayachi, S. (43) Khalid, M.; Ali, A.; Jawaria, R.; Asghar, M. A.; Asim, S.; Khan, M.
Photophysical and nonlinear optical properties of para-substituted U.; Hussain, R.; ur Rehman, M. F.; Ennis, C. H. J.; et al. First principles
nitrobenzofurazan: A comprehensive DFT investigation. J. Photochem. study of electronic and nonlinear optical properties of A-D-p-A and D-
Photobiol., A 2023, 443, No. 114850. A-D-p-A configured compounds containing novel quinoline−carbazole
(24) Raissi, H.; Chérif, I.; Aribi, I.; Ayachi, H.; Haj Said, A.; Ayachi, S.; derivatives. RSC Adv. 2020, 10 (37), 22273−22283.
Boubaker, T. Structure-property relationships in para-substituted (44) Tahir, M. N.; Mirza, S. H.; Khalid, M.; Ali, A.; Khan, M. U.;
nitrobenzofurazans: electrochemical, optical, and theoretical analysis. Braga, A. A. C. Synthesis, single crystal analysis and DFT based
Chem. Pap. 2022, 76, 4059−4080. computational studies of 2,4-diamino-5-(4-chlorophenyl)-6-ethylpyr-
(25) Bem, M.; Radutiu, A. C.; Voicescu, M.; Caproiu, M. T.; Draghici, im idin-1-ium 3,4,5- trihydroxybenzoate -methanol (DETM). J. Mol.
C.; Maganu, M.; Enache, C.; Constantinescu, T.; Balaband, A. T. 7- Struct. 2019, 1180, 119−126.
nitrobenzo[c] [1, 2, 5] oxadiazole (nitrobenzofurazan) derivatives with (45) Ashfaq, M.; Tahir, M. N.; Kuznetsov, A.; Mirza, S. H.; Khalid, M.;
a sulfide group at the 4-position. Synthesis and physical properties. Rev. Ali, A. DFT and single crystal analysis of the pyrimethamine-based
Roum. Biochim. 2018, 63 (2), 149−155. novel co-crystal salt: 2,4-diamino-5-(4-chloro-phenyl)-6-ethylpyrimi-
(26) Frisch, M. J.et al. Gaussian 09, revision A.01; Gaussian Inc.: din-1- ium:4-hydroxybenzoate:methanol:hydrate (1:1:1:1)
Wallingford, 2009. (DEHMH). J. Mol. Struct. 2020, 1199, No. 127041.
(27) Tomasi, J.; Mennucci, B.; Cancès, E. The IEF version of the PCM (46) Shafiq, I.; Amanat, I.; Khalid, M.; Asghar, M. A.; Baby, R.;
solvation method: an overview of a new method addressed to study Ahmed, S.; Alshehri, S. M. Influence of azo-based donor modifications
molecular solutes at the QM ab initio level. J. Mol. Struct. 1999, 464, on nonlinear optical amplitude of D-π-A based organic chromophores:
211−226. A DFT/TD-DFT exploration. Synth. Met. 2023, 297, No. 117410.
(28) Becke, A. D. Density-functional thermochemistry. III. The role of (47) Lawal, M. M.; Govender, T.; Maguire, G. E.; Honarparvar, B.;
exact exchange. J. Chem. Phys. 1993, 98, 5648−5652. Kruger, H. G. Mechanistic investigation of the uncatalyzed esterifcation
(29) Lee, C.; Yang, W.; Parr, R. G. Development of the Colle-Salvetti reaction of acetic acid and acid halides with methanol: a DFT study. J.
correlation-energy formula into a functional of the electron density. Mol. Model. 2016, 22, No. 235.
Phys. Rev. B 1988, 37, 785−789. (48) Gummidi, L.; Kerru, N.; Ibeji, C. U.; Singh, P. Crystal structure
(30) Bouazzi, D.; Chérif, I.; Mehri, A.; Touati, H.; Caccamo, M. T.; and DFT studies of (E)-1-(4-fluorophenyl)-3-(1H-indol-1-yl)-4-
Magazù, S.; Ayachi, S.; Clacens, J.-M.; Badraoui, B. A joint experimental styrylazetidin-2-one. J. Mol. Struct. 2019, 1187, 50−58.
and theoretical study on Structural, Vibrational and morphological (49) Khan, M. U.; Mehboob, M. Y.; Hussain, R.; Afzal, Z.; Khalid, M.;
properties of newly synthesized nanocomposites involving Hydrox- Adnan, M. Designing spirobifullerene core based three-dimensional
yapatite-alt-Polyethylene Glycol (HAP/PEG). J. Mol. Liq. 2023, 390, cross shape acceptor materials with promising photovoltaic properties
No. 123192. for high-efficiency organic solar cells. Int. J. Quantum Chem. 2020, 120,
(31) Dennington, R.; Keith, T.; Millam, J. GaussView, version 5.0.8; No. e26377.
Semichem Inc.: Shawnee Mission KS, 2009. (50) Khalid, M.; Khan, M. U.; Razia, E.; Shafiq, Z.; Alam, M. M.;
(32) Petersilka, M.; Gossmann, U. J.; Gross, E. K. U. Excitation Imran, M.; Akram, M. S. Exploration of efficient electron acceptors for
energies from time-dependent density-functional theory. Phys. Rev. Lett. organic solar cells: Rational design of indacenodithiophene based non-
1996, 76, 1212−1215. fullerene compounds. Sci. Rep. 2021, 11, No. 19931.

9908 https://doi.org/10.1021/acs.jpca.3c04277
J. Phys. Chem. A 2023, 127, 9895−9910
The Journal of Physical Chemistry A pubs.acs.org/JPCA Article

(51) Parr, R. G.; Szentpaly, L. V.; Liu, S. Electrophilicity Index. J. Am. (71) Bader, R. F. W.; Austen, M. A. Properties of atoms in molecules:
Chem. Soc. 1999, 121, 1922−1924. atoms under pressure. J. Chem. Phys. 1997, 107, 4271−4285.
(52) Parr, R. G.; Yang, W. Density Functional Theory of Atoms and (72) Tariq, S.; Khalid, M.; Raza, A. R.; Rubab, S. L.; de
Molecules; Oxford University Press: New York, Oxford, 1989. AlcântaraMorais, S. F.; Khan, M. U.; Tahir, M. N.; Braga, A. A. C.
(53) Park, J. C.; Nam, Y. S. Controlling surface defects of non- Experimental and computational investigations of new indole
stoichiometric copper-indium-sulfide quantum dots. J. Colloid Interface derivatives: A combined spectroscopic, SC-XRD, DFT/TD-DFT and
Sci. 2015, 460, 173−180. QTAIM analysis. J. Mol. Struct. 2020, 1207, No. 127803.
(54) Meinardi, F.; Daniel, H. M.; Carulli, F.; Colombo, A.; Velizhanin, (73) Khalid, M.; Ali, A.; Abid, S.; Tahir, M. N.; Khan, M. U.; Ashfaq,
K. A.; Makarov, N. S.; Simonutti, R.; klimov, V. I.; Brovelli, S. Highly M.; Imran, M.; Ahmad, A. Facile Ultrasound-Based Synthesis, SC-XRD,
efficient large-area colourless luminescent solar concentrators using DFT Exploration of the Substituted Acyl-Hydrazones: An Exper-
heavy-metal-free colloidal quantum dots. Nat. Nanotechnol. 2015, 10, imental and Theoretical Slant towards Supramolecular Chemistry.
878−885. ChemistrySelect 2020, 5 (47), 14844−14856.
(55) Valeur, B. Molecular Fluorescence: Principles and Applications; (74) Ali, A.; Khalid, M.; Abid, S.; Tahir, M. N.; Iqbal, J.; Ashfaq, M.;
Wiley-VCH: Berlin, Germany, 2001. Kanwal, F.; Lu, C.; Rehman, M. F. Green Synthesis, SC-XRD, Non-
(56) Heberer, H.; Matschiner, H. UV−VIS− und IR-spektroskopi- Covalent Interactive Potential and Electronic Communication via DFT
sche Untersuchungen an N-substituierten 4-Amino-7-nitrobenz-2,1,3- Exploration of Pyridine-Based Hydrazone. Crystals 2020, 10, No. 778.
oxadiazolen. J. Prakt. Chem. 1986, 328, 261−274. (75) Ali, A.; Khalid, M.; Ashfaq, M.; Malik, A. N.; Tahir, M. N.; Assiri,
(57) Ans, M.; Iqbal, J.; Eliasson, B.; Saif, M. J.; Javed, H. M. A.; Ayub, M. A.; Imran, M.; de AlcântaraMorais, S. F.; Braga, A. A. C. Preparation,
K. Designing of non-fullerene 3D star-shaped acceptors for organic QTAIM and Single-Crystal Exploration of the Pyrimethamine-Based
solar cells. J. Mol. Model. 2019, 25, No. 129. Co-Crystal Salts with Substituted Benzoic Acids. ChemistrySelect 2022,
(58) Maddalena, F.; Falco, C.; Caironi, M.; Natali, D. Assessing the 7 (17), No. e202200349.
width of Gaussian density of states in organic semiconductors. Org. (76) Espinosa, E.; Molins, E.; Lecomte, C. Hydrogen bond strengths
Electron. 2015, 17, 304−318. revealed by topological analyses of experimentally observed electron
(59) O’Boyle, N. M.; Tenderholt, A. L.; Langner, K. M. cclib: A library densities. Chem. Phys. Lett. 1998, 285, 170−173.
for package-independent computational chemistry algorithms. J. (77) Rozas, I.; Alkorta, I.; Elguero, J. Behavior of Ylides Containing N,
Comput. Chem. 2008, 29, 839−845. O, and C Atoms as Hydrogen Bond Acceptors. J. Am. Chem. Soc. 2000,
(60) Chen, M.; Waghmare, U. V.; Friend, C. M.; Kaxiras, F. A density
122, 11154−11161.
functional study of clean and hydrogen-covered α-MoO3 (010): (78) Koch, U.; Popelier, P. L. A. Characterization of C-H-O Hydrogen
Electronic structure and surface relaxation. J. Chem. Phys. 1998, 109,
Bonds on the Basis of the Charge Density. J. Phys. Chem. A 1995, 99,
6680−6854.
9747−9754.
(61) Liu, S.; Zhao, Y.; Zhang, C.; Lin, L.; Li, Y.; Song, Y. the novel
(79) Hirshfeld, F. L. Bonded-atom fragments for describing molecular
excited state intramolecular proton transfer broken by intermolecular
charge densities. Theor. Chim. Acta. 1977, 44, 129−138.
hydrogen bonds in HOF system. Spectrochim. Acta, Part A 2019, 219,
(80) Spackman, M. A.; Jayatilaka, D. Hirshfeld surface analysis.
164−172.
CrystEngComm 2009, 11, 19−32.
(62) Johnson, E. R.; Shahar, K.; Paula, M. S.; Julia, C. G.; Cohen, A. J.;
(81) McKinnon, J. J.; Jayatilaka, D.; Spackman, M. A. Towards
Weitao, Y. Revealing Noncovalent Interactions. J. Am. Chem. Soc. 2010,
Quantitative Analysis of Intermolecular Interactions with Hirshfeld
132 (2010), 6498−6506.
(63) Alotaibi, M. T. Noncovalent interaction stabilizes the 2, 4- Surfaces. Chem. Commun. 2007, 37, 3814−3816.
Dinitrophenylhydrazone Derivatives over g-C3N4 surface to enhance (82) Ashfaq, M.; Khalid, M.; Tahir, M. N.; Ali, A.; Arshad, M. N.; Asiri,
optical properties: synthesis, characterization, and DFT investigation. J. A. M. Synthesis of Crystalline Fluoro-Functionalized Imines, Single
Mol. Struct. 2020, 1214, No. 128192. Crystal Investigation, Hirshfeld Surface Analysis, and Theoretical
(64) Boto, R. A.; Piquemal, J. P.; Contreras-García, J. Revealing strong Exploration. ACS Omega 2022, 7 (11), 9867−9878.
interactions with the reduced density gradient: a benchmark for (83) Khalid, M.; Ali, A.; Abid, S.; Tahir, M. N.; Khan, M. U.; Ashfaq,
covalent, ionic and charge-shift bonds. Theor. Chem. Acc. 2017, 136, M.; Imran, M.; Ahmad, A. Facile Ultrasound-Based Synthesis, SC-XRD,
No. 139. DFT Exploration of the Substituted Acyl-Hydrazones: An Exper-
(65) Silvi, B.; Savin, A. Classification of chemical bonds based on imental and Theoretical Slant towards Supramolecular Chemistry.
topological analysis of electron localization functions. Nature 1994, ChemistrySelect 2020, 5, 14844−14856.
371, 683−686. (84) Ali, A.; Khalid, M.; Abid, S.; Tahir, M.; Iqbal, J.; Ashfaq, M.;
(66) Arulaabaranam, K.; Mani, G.; Muthu, S. Computational Kanwal, F.; Lu, C.; Rehman, M. Green synthesis, SC-XRD, non-
assessment on wave function (ELF, LOL) analysis, molecular covalent interactive potential andelectronic communication via DFT
confirmation and molecular docking explores on 2-(5-Amino2- exploration of pyridine-basedhydrazone. Crystals 2020, 10 (9),
Methylanilino)-4-(3-pyridyl) pyrimidine. Chem. Data Collect. 2020, No. 778.
29, No. 100525. (85) McKinnon, J. J.; Spackman, M. A.; Mitchell, A. S. Novel tools for
(67) Prasana, J. C.; Muthu, S.; Abraham, C. S. Molecular docking visualizing and exploring intermolecular interactions in molecular
studies, charge transfer excitation and wave function analyses (ESP, crystals. Acta Crystallogr., Sect. B: Struct. Sci. 2004, 60, 627−668.
ELF, LOL) on valacyclovir: a potential antiviral drug. Comput. Biol. (86) Spackman, M. A.; Byrom, P. G. A novel definition of a molecule
Chem. 2019, 78, 9−17. in a crystal. Chem. Phys. Lett. 1997, 267, 215−220.
(68) Gadre, S. R.; Suresh, C. H.; Mohan, N. Electrostatic Potential (87) Jayatilaka, D.; Wolff, S. K.; Grimwood, D. J.; McKinnon, J. J.;
Topology for Probing Molecular Structure, Bonding Reactivity. Spackman, M. A. CrystalExplorer: a tool for displaying Hirshfeld
Molecules 2021, 26, No. 3289. surfaces and visualising intermolecular interactions in molecular
(69) Sevvanthi, S.; Muthu, S.; Raja, M. Molecular docking, vibrational crystals. Acta Crystallogr., Sect. A: Found. Crystallogr. 2006, 62, No. s90.
spectroscopy studies of (RS)-2-(tert-Butylamino)-1-(3-chlorophenyl)- (88) Prasad, P. N.; Williams, D. J. Introduction to Nonlinear Optical
propan-1-one: A potential Adrenaline uptake inhibitor. J. Mol. Struct. Effects in Molecules and Polymers; Wiley: New York, 1991.
2018, 1173, 251−260. (89) Geskin, V. M.; Lambert, C.; Brédas, J. L. Origin of High Second-
(70) Saral, A.; Sudha, P.; Muthu, S.; Sevvanthi, S.; Irfan, A. Molecular and Third-Order Nonlinear Optical Response in Ammonio/Borato
structure spectroscopic Elucidation, IEFPCM solvation (UV− Vis, Diphenylpolyene Zwitterions: the Remarkable Role of Polarized
MEP, FMO, NBO, NLO), molecular docking and biological assess- Aromatic Groups. J. Am. Chem. Soc. 2003, 125, 15651−15658.
ment studies of lepidine (4-Methylquinoline). J. Mol. Liq. 2022, 345, (90) Lokhande, P. K. M.; Patil, D. S.; Kadam, M. M.; Sekar, N.
No. 118249. Theoretical Investigation of Optical and Nonlinear Optical (NLO)

9909 https://doi.org/10.1021/acs.jpca.3c04277
J. Phys. Chem. A 2023, 127, 9895−9910
The Journal of Physical Chemistry A pubs.acs.org/JPCA Article

Properties of 3-Azabenzanthrone Analogues: DFT and TD-DFT

Approach. ChemistrySelect 2019, 4, 10033−10045.
(91) Tillekaratne, A. D.; de Silva, R. M.; de Silva, K. M. N. Push-Pull
Porphyrins as Non-Linear Optical Materials: Ab Initio Quantum
Chemical Calculations. J. Mol. Struct.: THEOCHEM 2003, 638, 169−
176.
(92) Kleinman, D. A. Nonlinear Dielectric Polarization in Optical
Media. Phys. Rev. 1962, 126, 1977−1979.
(93) Janaki, A.; Balachandran, V.; Lakshmi, A. First order molecular
hyperpolarizabilities and intramolecular charge transfer from vibra-
tional spectra of NLO material: 2,6-dichloro-4- nitraniline. Ind. J. Pure
Appl. Phys. 2013, 51, 601−614.
(94) Khalid, M.; Khan, M. U.; Shafiq, I.; Hussain, R.; Mahmood, K.;
Hussain, A.; Jawaria, R.; Hussain, A.; Imran, M.; Assiri, M. A. NLO
Potential Exploration for D-p-A Heterocyclic Organic Compounds by
Incorporation of Various p-Linkers and Acceptor Units. Arab. J. Chem.
2021, 14 (8), No. 103295.
(95) Khalid, M.; Khan, M. U.; Shafiq, I.; Hussain, R.; Ali, A.; Imran,
M.; Braga, A. A. C.; Ur Rehman, M. F.; Akram, M. S. Structural
modulation of π-conjugated linkers in D−π−A dyes based on
triphenylamine dicyanovinylene framework to explore the NLO
properties. R. Soc. Open Sci. 2021, 8, No. 210570.
(96) Khalid, M.; Shafiq, I.; Mahmood, K.; Hussain, R.; Ur Rehman, M.
F.; Assiri, M. A.; Imran, M.; Akram, M. S. Effect of different end-capped
donor moieties on non-fullerenes based non-covalently fused-ring
derivatives for achieving high-performance NLO properties. Sci. Rep.
2023, 13, No. 1395.
(97) Khalid, M.; Arshad, M. N.; Murtaza, S.; Shafiq, I.; Haroon, M.;
Asiri, A. M.; de AlcântaraMorais, S. F.; Braga, A. A. Enriching NLO
Efficacy via Designing Non-Fullerene Molecules with the Modification
of Acceptor Moieties into ICIF2F: An Emerging Theoretical Approach.
RSC Adv. 2022, 12 (21), 13412−13427.
(98) Yang, L. M.; Liu, Y.; Man, L. M.; Zhou, J. R.; Liu, X. P.; Ni, C. L.
Crystal structure,vibrational spectra, optical properties and density
functional theoretical approach of [Bz4-NH 2 Py] 4 [CdCl 4 ] 2. H 2 O.
Vib. Spectrosc. 2017, 93, 23−28.
(99) Cassidy, C.; Halbout, J.; Donaldson, W.; Tang, C. Nonlinear
optical properties of urea. Opt. Commun. 1979, 29, 243−246.
(100) Machado, D. F. S.; Lopes, T. O.; Lima, I. T.; da Silva Filho, D.
A.; de Oliveira, H. C. Strong Solvent Effects on the Nonlinear Optical
Properties of Z and E Isomers from Azo-Enaminone Derivatives. J. Phys.
Chem. C 2016, 120 (31), 17660−17669.
(101) Günter, P. Nonlinear Optical Effects and Materials, 4th ed.;
Springer: Berlin, 2000.

9910 https://doi.org/10.1021/acs.jpca.3c04277
J. Phys. Chem. A 2023, 127, 9895−9910