Supplementary Material for
H-atom reactivity as a function of temperature in
solid parahydrogen: The H + N2O reaction
Fredrick M. Mutunga, Shelby E. Follett and David T. Anderson
Department of Chemistry, University of Wyoming, Laramie, WY
82071
Email:
[email protected] 1. Experimental details
The N2O doped pH2 crystals are prepared using the rapid vapor
deposition method of Fajardo and Tam. 1,
deposition of independent gas flows of
15
The crystal is grown by co-
N218O and pH2 onto a pre-cooled
BaF2 optical substrate held at ~2.5 K within a sample-in-vacuum liquid-He
cryostat.
We estimate the N2O dopant concentrations based on the
measured flow rates of dopant and pH 2 gas into the cryostat during
deposition. For these studies the dopant concentration ranged from 20 to 70
ppm. The pH2 solids are prepared by enriching normal-H2 gas to greater than
99.97% pH2 enrichment levels using a variable temperature ortho/para
converter operated near 14.0 K. The orthohydrogen (oH 2) concentration in
the sample can be checked using the integrated intensity of the oH 2-induced
Q1(0) feature1 and the measured crystal thickness. 3 The temperature of the
sample is measured using two Si-diode sensors; one is mounted (T A) to the
cold tip of the helium cryostat and the other (T B) is mounted to the Au-plated
oxygen-free-high-conductivity Cu substrate holder at the point furthest from
the cold tip. All the reported temperatures are using TB.
The H-atoms are generated as by-products in the 193 nm in situ
photolysis of the
15
N218O precursor.
The unfocused 193 nm output of a
broadband ArF excimer laser (Gam Laser EX5) with 8 ns pulse duration is
directed at an angle of 45 with respect to the surface normal of the BaF 2
optical substrate. The FTIR beam is focused with 8 off-axis parabolic mirrors
through the sample at normal incidence to the BaF 2 optical substrate in a
transmission optical setup.
This optical setup permits FTIR spectra to be
recorded within the photolysis region either during or immediately after 193
nm irradiation. The laser fluences in these experiments, measured with a
power meter after an adjustable iris located in front of the photolysis window
on the cryostat, range from 60 to 75 J cm-2 pulse-1 and we used the highest
250 Hz repetition rate of the laser.
High-resolution rapid scan FTIR spectroscopy (e.g., acquisitions times
of 290 sec for 16 co-added scans at 0.03 cm -1 resolution) is performed on the
sample using a FTIR spectrometer (Bruker IFS 120HR) equipped with a
glowbar source and Ge-coated KBr beamsplitter.
For all the kinetic
measurements we use a liquid nitrogen cooled HgCdTe detector to record
spectra from 700 to 4500 cm -1.
The concentration of the cis and trans
isomers of H15N15N18O are measured from the integrated intensity of the 2
(NN stretch) absorptions near 1575 cm -1 using the following integration
protocols. The cis peak is integrated from 1573.5 to 1576.5 cm -1 and the
trans peak from 1577.5 to 1580.5 cm -1. We calculate the concentration in
units of parts per million (ppm) using the following equation,
[X ]
2.303 log 10 ( I / I 0 )d~
V0 (1x10 6 )
(1)
where X is cis or trans, is the integrated absorption coefficient, l is the IR
pathlength through the crystal, and V0 is the molar volume4 of solid pH2 at
liquid helium temperatures (23.16 cm3 mol-1). The value of l is determined
for each sample using the IR spectroscopic method developed by Fajardo. 3
The values used are 367.3 and 240.2 km mol -1 for the cis and trans 2
modes, respectively.
Note these values are for the H 15N15N18O isotopomer
and were provided to us by Professor Kirk A. Peterson.5
2. Spectroscopic results
We made the cis- and trans-H15N15N18O spectroscopic assignments
based on the agreement with the peak positions of Xe matrix isolation
results6, 7 and full anharmonic calculations of the vibrational frequencies and
isotopic shifts.8
The measured peak positions and isotopic shifts are
presented in Tables S1 and S2. We tested these assignments using binary
intensity correlation plots which are shown in Figures S1 and S1.
These
correlation plots demonstrate that there are two distinct product species and
that the peak assignments to a given isomer are internally consistent.
Shown in Figure S3 is a series of IR spectra recorded during the course of a
single photolysis experiment on a
15
N218O doped pH2 solid conducted at
1.81(2) K showing the corresponding cis- and trans-H15N15N18O peaks used to
monitor the chemistry. We chose to use the 2 mode (NN stretch) to monitor
the concentration of cis- and trans-H15N15N18O.
Trace (a) in Figure S3 is
recorded prior to photolysis and shows no discernible IR absorptions in this
small window between 1570 and 1585 cm-1. Trace (b) is recorded beginning
immediately after the 10 minute photolysis of the sample at 1.84 K and
shows a small peak at 1574.91 cm-1 due to the slight production of cis during
low temperature photolysis. Trace (c) is recorded 486.4 minutes after trace
(b) while maintaining the sample at a constant temperature of 1.81(2) K.
Clearly there is significant growth in the intensity of the two peaks
corresponding to cis- and trans-H15N15N18O. We use the integrated intensity
of these two peaks combined with the measured thickness of the sample to
calculate the concentration of both isomers.
Note that the FTIR spectra
shown in Figure S3 are for the experiment displayed in Figure 1.
Table S1. Measured peak positions and isotopic shifts () all in cm-1 for cisHNNO.
mode
14
N216O/Xe
a
1 NH str
2 NN str
3 NO str
4 HNN
bend
3158
1623.7
1273.4
14
N216O/p
H2
3069.08
1629.28
1282.48
15
N218O/p
H2
1574.91
1255.31
(Expt.
)
(Calc.)
b
-6.7
-55.4
-26.5
-54.37
-27.17
1166.9
-40.0
In a Xe matrix, Ref. 7.
Calculated isotopic shift, Ref. 8.
Table S2. Measured peak positions and isotopic shifts () all in cm-1 for
trans-HNNO.
mode
1 NH str
2 NN str
3 NO str
4 HNN
bend
14
N216O/Xe
a
3254.0
1628.9
1294.5
1213.4
14
N216O/p
H2
3280.29
1634.52
1299.19
1221.27
15
N218O/p
H2
3273.17
1578.82
1272.26
1186.91
(Expt.
)
-7.12
-55.70
-26.93
-34.36
(Calc.)
b
-7.1
-57.8
-35.3
-31.1
In a Xe matrix, Ref. 7.
Calculated isotopic shift, Ref. 8.
0.07
cis
integrated intensity / cm
-1
0.06
0.05
3 NO stretch
0.04
0.03
0.02
0.01
0.00
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
-1
cis 2 NN stretch integrated intensity / cm
Figure S1. Binary intensity correlation plot for cis-H15N15N18O.
Figure S2. Binary intensity correlation plot for trans-H15N15N18O.
0.5
trans
log10(I0/I) / abs
0.4
cis
0.3
0.2
0.1
0.0
(c)
(b)
(a)
1570
1575
1580
1585
wavenumber / cm -1
Figure S3. Representative IR spectra displaying the 2 (NN stretch) peaks of
cis- and trans-H15N15N18O at various steps in a low temperature reaction study
on a 0.24(2) cm thick, 23 ppm 15N218O doped pH2 sample. Trace (a) is
recorded at 1.82 K before photolysis, trace (b) is recorded (16 co-added
scans, 290 sec, 0.03 cm-1 resolution) at 1.83 K right after photolysis, and
trace (c) is recorded 486.4 min after trace (b) while the sample is maintained
at a constant temperature of 1.81(2) K.
Table S3. Kinetic parameters determined from fit to data in Figure 1.
parameter
A10 / ppm
A20 / ppm
k1 /10-3
min-1
k2 /10-3
min-1
R2
cisa
6.01(24)
(28)
0.0440(28)
transb
2.60(22)
1.413(46)
1.67(22)
8.63(18)
12.1(27)
0.999162
0.999773
0.000(8)
f (t ) A20 exp( k 2 t )
k1 A10
exp( k 2t ) exp( k1t )
k1 k 2
cis function:
trans function:
k1
f (t ) A10 1 exp( k1t )
exp( k1t ) exp( k 2t ) A20 1 exp( k 2t )
k 2 k1
REFERENCES
[1]
S. Tam, and M. E. Fajardo, Rev. Sci. Instrum. 70, 1926 (1999).
[2]
S. Tam, and M. E. Fajardo, Appl. Spectrosc. 55, 1634 (2001).
[3]
M. E. Fajardo, in Physics and Chemistry at Low Temperatures, edited by L.
Khriachtchev (Pan Stanford Publishing Pte. Ltd., Singapore, 2011), pp. 167.
[4]
I. F. Silvera, Rev. Mod. Phys. 52, 393 (1980).
[5]
K. A. Peterson, (private communication, 2012).
[6]
K. M.-R. Isokoski, in Ph.D. Thesis (University of Helsinki, Helsinki, 2008), p. 69.
[7]
S. L. Laursen, A. E. Delia, and K. Mitchell, J. Phys. Chem. A 104, 3681 (2000).
[8]
K. A. Peterson, and J. S. Francisco, J. Chem. Phys. 134, 084308 (2011).
