DOI: 10.1002/slct.

201600587 Communications

z Electro, Physical & Theoretical Chemistry

Negative Absorption Peaks in Ultraviolet–Visible Spectrum

of Water
Yan Ji,*[a] Zhi Ji,[b] Meihuan Yao,[a] Ying Qian,[c] and Yufeng Peng[d]

Ultraviolet-visible absorption spectra exhibit absorption that is A ¼ ebc ð2Þ

under the base line, which we propose is negative absorption
(NA) or negative absorption emission (NAE). The UV-visible NAE where A is the measured absorbance in absorbance units
of water, ethanol, and chloroform was illustrated by trans- (a.u.), b is the path length through the sample (cm), and c is
mittance curves, reflectivity curves, and fluorescence excitation/ the concentration of the absorbing species. For each species
emission spectra. To explain this phenomenon, the TD_DFT and wavelength, e, is a known constant referred to as the molar
theory was used to calculate the emission states of the sam- absorptive or extinction coefficient, which is used to show the
ples. A laser transmission experiment confirmed the NAE phe- absorption ability of the sample.[4]
nomenon. It was concluded that NAE was a type of emission Research on water has been performed in many areas. Wa-
produced by the sample. The NAE of water has significant im- ter environmental resources have been studied,[6] including
plications for life on earth, which will interest researchers in drinking water, geographic attribution, and even research on
physics, chemistry, and biology. the presence of water on other planets for future human space
activity. Physics and chemistry research on water, such as mo-
lecular structure studies,[7] quantum chemical research,[8] and
research on the spectrum (absorption) of water,[9] is extensive.
The intramolecular interactions of water have also been ex-
Introductions
plored. In addition, biology-related water research has been
Ultraviolet-visible (UV-vis) absorption spectra show how sam- performed,[10] which shows that water is critical for life on earth.
ples absorb light in the ultraviolet or visible region and meas- This communication reports the phenomenon of UV-vis ab-
ure the transitions from the ground state to the excited state.[1] sorption that is less than zero, which is proposed to be UV-vis
UV-Vis spectrophotometers measure the ultraviolet-visible ab- negative absorption (NA) or negative absorption emission
sorbance. UV-Vis spectroscopy measures the intensity of light (NAE). Water and other solvents were tested and shown to
passing through a sample (IT), and compares this intensity to have NAE phenomena, which might aid in future water related
the intensity of light before it passes through the sample (I0). research.
The ratio IT/I0 is called the transmittance (T). The absorbance (A)
is based on the transmittance (Eqn. 1):[2]
Results and Discussion
A ¼ -log ðTÞ ð1Þ
UV-vis negative absorption
The Lambert–Beer law (Eqn.2) describes the relationship be- The UV-vis absorption spectra of water, ethanol, chloroform,
tween the concentration, the sample cell, and the absorb- DMF, and DMSO were measured and are shown in Figures 1–5.
ance:[3] The typical absorption of water was in the UV range at
200–245 nm. The absorption from 250 to 900 nm was less than
[a] Prof. Assoc. Dr. Y. Ji, Dr. M. Yao zero and was proposed to be negative absorption (NA). The
School of Chemistry and Chemical Engineering UV-vis absorption spectra of water, ethanol and chloroform ex-
Henan Normal University hibited this NA phenomenon. The DMF and DMSO presented
Xinxiang, 453007, Henan, China
normal absorption spectra without this negative absorption
E-mail: [email protected]
[b] Dr. Z. Ji phenomenon.
College of Chemistry and Materials Engineering The common absorption was categorized as A > 0, A = 0
Guiyang University where no absorption was observed, and A < 0, which was pro-
Guiyang, 550005, Guizhou, China
posed to be negative absorption. The negative absorption was
[c] Prof. Y. Qian
School of Chemistry and Chemical Engineering under the base line (zero line). In negative absorption the
Southeast University emergent light intensity was larger than the incident light in-
Nanjing 211189, Jiangsu, China tensity (I0 < IT), which means that T=IT/I0 > 100 %. The trans-
[d] Prof. Y. Peng
mittance curves of water, ethanol, and chloroform were meas-
College of Physics Electronic and Engineering
Henan Normal University ured (Figure 1-3) and show that T% > 100 %. From these data,
Xinxiang, 453007, Henan, China an absorbance of A < 0 can be deduced (Figure 6) based on

ChemistrySelect 2016, 1, 3443 – 3448 3443  2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
 Communications

Figure 1. The UV-vis absorption spectrum of water (range: 200 nm Figure 4. The UV-vis absorption spectrum of DMF. (range: 200 nm 1000 nm,
1000 nm, room temperature)[11] room temperature)[11]

Figure 2. The UV-vis absorption spectrum of ethanol (range: 200 nm Figure 5. The UV-vis absorption spectrum of DMSO. (range: 200 nm
1000 nm, room temperature)[11] 1000 nm, room temperature)[11]

Figure 3. The UV-vis absorption spectrum of chloroform (range: 200 nm Figure 6. The transmittance curves of water, ethanol, and chloroform. (range:
1000 nm, room temperature)[11] 200 nm 1000 nm, room temperature)[11]

ChemistrySelect 2016, 1, 3443 – 3448 3444  2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
 Communications
Eqn. 1. The reflectivity (R) of the sample was > 100 % (Figure 7), sorption is difficult to understand and is easily ignored, often
which shows that the reflected light was greater than the in- regarded as a mistake or error in the measurement.

Quantum chemical calculation

The time-dependent density functional theory (TD_DFT) b3lyp/
6-31 g method in the Gaussian 09[11] software package was
used to calculate the emission states of water, ethanol, and
chloroform to test the emission behavior of the samples using
quantum chemical theory. The calculated data in Table 1 show
that water, ethanol, and chloroform all have emissions in the
visible light range, which may explain the negative absorption
as a result of the emission of the samples. The fluorescence
emission spectra of water, ethanol, and chloroform were meas-
ured and are shown in Figure 9. The water sample has an emis-

Figure 7. The reflectivity curves of water, ethanol, and chloroform. (range:

200 nm 1000 nm, room temperature)[11]

Figure 9. Fluorescence emission spectra of water, ethanol, and chloroform.

(range: 480–850 nm, excitation wavelength 467 nm, room temperature)[17]

Figure 8. The schematic of ultraviolet-visible (UV-vis) negative absorption sion peak at 556 nm, which is close to the transition energy ob-
(NA) or negative absorption emission (NAE) phenomena. (A is absorbance, T tained from the calculated data (S1!S0: 534.19 nm) in Table 1.
is transmittance)
These calculations and spectra show that water has emission
behavior at UV-visible wavelengths. Figure 10 presents the fluo-
rescence excitation spectra of water, ethanol, and chloroform,
cident light. The reasonable explanation for the negative ab- which show that fluorescence emission was high at
sorption is a type of emission phenomenon. The incident light 200–300 nm and weak at 300–800 nm. Figure 11 shows the
and surrounding environment excited the sample to produce three-dimensional fluorescence spectrum of water, which illus-
emission, thus forming a negative absorption (NA) or negative trates the whole fluorescent landscape of water in the
absorption emission (NAE) phenomenon. NAE might be due to 200–800 nm range. Figure 11 shows that excitation wave-
the light exciting samples from ground states to lower molec- lengths in the 200–300 nm UV range excited the water sample
ular orbitals, or from ground states to excited states and then and produced fluorescence emission in the 200–800 nm range,
back to lower molecular orbitals, thus producing an emission which indicates that high amounts of UV light energy are trans-
that results in A < 0 (Figure 1-3) or T% > 100 % (Figure 6). The ferred to visible and infrared light. The absorption of UV light
light source acts on the samples, exciting a larger energy emis- and the transfer to longer wavelengths of light energy show
sion, which results in emergent light or emission light energy NAE in the water UV-vis absorption spectra.
being more than the incident light or excitation light energy. Materials have two optical actions: one is down-conversion
The surrounding environment or intramolecular energy or quantum cutting (short wavelength absorption, long wave-
must participate in this process to maintain conservation of en- length emission);[12] the other is up-conversion (long wave-
ergy. UV-Vis spectroscopy is a common optical test to research length absorption, short wavelength emission).[13] From Fig-
the ability of a sample to absorb light. The negative UV-vis ab- ures 1 and 11, the NAE of water was the down-conversion

ChemistrySelect 2016, 1, 3443 – 3448 3445  2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
 Communications

Table 1. The calculated emission spectra of water, ethanol, and chloroform in gas phase vacuum calculated by the Table 1 presents the T1!T0
TD_DFT b3lyp/6-31 g method. triplet emission states of water.
Electron Energy Calculated Main transition Oscillator strength f
T1!T0 were triplet transitions
transitiona (eV) wavelength (nm) Configuration b that did not take part in fluo-
rescence emission. The T1!T0
Water S1!S0 2.3210 534.19 LUMO!HOMO: 0.11454 0.0011
S1!S0 10.033 123.57 LUMO!HOMO-2: 0.10527 0.9660
energy level transitions take
S1!S0 1.8370 674.94 LUMO!HOMO-1: 0.18833 0.0011 place through energy transfer.
T1!T0 2.7856 445.10 LUMO!HOMO-2: 0.20439 0.0000 When T1!T0 transfers to one
LUMO + 1!HOMO-1: 0.14864 level, and this level further
T1!T0 1.2519 990.39 LUMO!HOMO:-0.10053 0.0000
T1!T0 4.7473 261.17 LUMO!HOMO-2: 0.10454 0.0000
changes to S1!S0 transitions,
Ethanol S1!S0 0.3386 3661.43 LUMO!HOMO-1: - 0.12726 0.0000 then fluorescence emission is
S1!S0 1.6214 764.67 LUMO!HOMO: 0.48337 0.0275 produced. The emission light
S1!S0 4.7282 262.22 LUMO!HOMO:0.24765 0.3189 energy from S1!S0 transitions
S1!S0 6.7737 183.04 LUMO!HOMO:0.11290 0.0164
T1!T0 2.6412 469.42 LUMO!HOMO:-0.17747 0.0000
also included T1!T0 transition
Chloroform S1!S0 3.6883 336.15 LUMO!HOMO-2:0.21222 0.2811 energy, which might explain
S1!S0 3.1242 396.85 LUMO!HOMO-2:0.10269 0.0547 how increased emergent light
S1!S0 4.5992 269.58 LUMO!HOMO-2:0.16968 0.3845 energy may come from addi-
S1!S0 2.9929 414.26 LUMO!HOMO-2:-0.21330 0.1325
T1!T0 0.5270 2352.76 LUMO!HOMO-1:0.14830 0.0000
tional energy level transition
T1!T0 0.5021 2469.09 LUMO!HOMO:-0.15627 0.0000 processes.
T1!T0 1.3376 926.91 LUMO!HOMO-2: 0.13951 0.0000
T1!T0 1.9236 644.54 LUMO!HOMO-4:-0.10573 0.0000

[a] S1!S0 was the (singlet) emission states and T1!T0 was the (triplet) emission states of water, ethanol, and
chloroform. b LUMO, lowest unoccupied molecular orbital; HOMO, highest occupied molecular orbital.

Figure 10. Fluorescence excitation spectra of water, ethanol, and chloroform. Figure 11. The three-dimensional fluorescence spectrum of water. (excitation
(excitation wavelength range: 200–800 nm, emission wavelength: 500 nm, wavelength range: 200–800 nm, emission wavelength range: 200–800 nm,
room temperature)[17] room temperature)[17]

process in the UV-visible region, which absorbed short wave-

length UV light and converted it to longer wavelength visible/
Laser experiment
infrared light or energy emission.
The negative absorption peaks represent emergent light in- A laser experiment was performed to test the incident power
tensity that is larger than that of the incident light. The in- and emergence power. The results of the laser test are listed in
creased light energy might come from the internal energy of Table 2. The laser wavelength was 405 nm. A quartz cuvette
the molecules. This increased energy might come from other was used to load the water sample. A blank quartz cuvette was
energy levels. The incident light excited more molecular energy first tested as a background reference. Several laser trans-
level transitions; the more excited energy level transitions and mission water samples were tested to record the incident light
emission resulted in emergent light that exceeded the incident intensity (Iin) and emergent light intensity (Iout) power. The (Iin-
light. In short, the incident light excited more molecular energy Iout)/Iin value of the quartz cuvette was 0.1182. The water sam-
to emission light and resulted in negative absorption peaks. ple (Iin-Iout)/Iin value ranged from 0.1179 to 0.1028. The ratio val-

ChemistrySelect 2016, 1, 3443 – 3448 3446  2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
 Communications

Table 2. Laser input and output power of water

Laser power 1 2 3 4 5 6
(103 W)

Water (Iin) 0.441 0.817 1.189 1.551 1.967 2.430

Water (Iout) 0.389 0.733 1.060 1.337 1.749 2.150
Quartz cuvette (Iin) 1.371
Quartz cuvette (Iout) 1.209
Water (Iin-Iout)/Iin 0.1179 0.1028 0.1084 0.1122 0.1108 0.1152
Quartz cuvette 0.1182
(Iin-Iout)/Iin

ues of the water samples were all smaller than those values of
the cuvette background. This means the light energy intensity
reduced by the empty cuvette was larger than that of the cuv-
ette loaded with water. From these data, it was concluded that
the water sample produced emergent light that was greater
than the incident light. This result is consistent with the UV-vis
absorption NAE phenomenon. The laser experiments confirm
the NAE phenomenon.
The negative absorption (NA) or negative absorption emis-
sion (NAE) are a type of energy or light emission that occurs
after absorption. The water as a solvent has NA or NAE, which
can act on the solute in solutions. There is energy transfer
(ET[14]) such as electronic energy transfer (EET[15]) or fluorescence
resonance energy transfer (FRET[16]) that depends on the inter-
action distance between the energy donor and energy accept-
or. EET occurs within 10 , while the FRET distance is typically Figure 12. Photograph of water taken in sunlight.

from 10 to 100 . Triplet–triplet energy transfers have an effi-

ciency distance of 10 . The NAE of water can act on a solute
within a range of 10 to 100  in solutions, and water transition The NAE phenomenon involved low power incident light
energy may transfer directly to the solute and affect the prop- producing high power emergent light, which can be defined as
erties of the solution. The NAE phenomena between the sol- Iout > Iin. We named this NAE phenomenon “Zeng Light”. The
utes and the solvent in solutions may be connected to light Chinese character spelling “Zeng” translated into English means
emission or energy transfer. NAE may constitute part of the sol- “add”. So Zeng Light (ZL) refers to emergent light power that is
vent effect, which acts on a solute. larger than incident light power when light is transmitted
The NAE of water can affect the behavior of solutions, opti- through materials.
cal physical properties, chemical reactions, and biological proc-
esses. The down-conversion of water has significance for all liv-
Conclusion
ing beings on earth. Plants, animals, and humans contain much
water in their bodies, which plays a role in many biochemical The negative absorption (NA) or negative absorption emission
reactions. Approximately 70–80 % of an animal’s weight is wa- (NAE) of matter is a newly observed phenomenon, which may
ter. In addition, more than 70 % of the earth’s surface is covered be due to emission behavior under excitation light. The NAE
in water. The negative absorption of water can reduce the phenomenon of water was determined by UV-vis absorption
damage of UV light to the body and convert UV light to low spectra and laser experiments. The NAE of water was observed
energy light to protect cells and tissues, which is a benefit for and has significant implications for life on earth. The NAE phe-
all living creatures. The NAE of water may be part of the reason nomenon will help researchers to understand water properties
that water in the environment makes earth fit for life, which better.
differentiates this planet from other planets. The NAE of water
can also provide energy to biomolecules and biological sys-
Acknowledgments
tems, which supports chemical reactions or biological proc-
esses in the body. The water in the atmosphere, seas, rivers and Henan Normal University Doctor Project Startup Science Foun-
lakes affects and modifies the weather, temperature, seasons, dation (QD15114)
and living environments on the earth, and the NAE phenomen-
on of water may be one of the important active reasons. Fig- Keywords: UV-vis absorption spectra · Negative absorption
ure 12 shows photographs of water. peaks · Water · Emission

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 Communications
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