Quantum Chemical Investigation of the Cold Water Dimer Spectrum in the First OH-Stretching Overtone Region Provides a New Interpretation
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Quantum Chemical Investigation of the Cold Water Dimer Spectrum in the First OH-Stretching Overtone Region Provides a New Interpretation. / Vogt, Emil; Simkó, Irén; Császár, Attila G.; Kjaergaard, Henrik G.
I: The journal of physical chemistry. A, Bind 127, Nr. 45, 2023, s. 9409-9418.Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › fagfællebedømt
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TY - JOUR
T1 - Quantum Chemical Investigation of the Cold Water Dimer Spectrum in the First OH-Stretching Overtone Region Provides a New Interpretation
AU - Vogt, Emil
AU - Simkó, Irén
AU - Császár, Attila G.
AU - Kjaergaard, Henrik G.
PY - 2023
Y1 - 2023
N2 - Intramolecular vibrational transition wavenumbers and intensities were calculated in the fundamental HOH-bending, fundamental OH-stretching, first OH-stretching-HOH-bending combination, and first OH-stretching overtone (ΔvOH = 2) regions of the water dimer's spectrum. Furthermore, the rotational-vibrational spectrum was calculated in the ΔvOH = 2 region at 10 K, corresponding to the temperature of the existing jet-expansion experiments. The calculated spectrum was obtained by combining results from a full-dimensional (12D) vibrational and a reduced-dimensional vibrational-rotational-tunneling model. The ΔvOH = 2 spectral region is rich in features due to contributions from multiple vibrational-rotational-tunneling sub-bands. Origins of the experimental vibrational bands depend on the assignment of the observed sub-bands. Based on our calculations, we assign the observed sub-bands, and our reassignment leads to new values for the vibrational band origins of the free donor and antisymmetric acceptor OH-stretching first overtones of ∼7227 and ∼7238 cm-1, respectively. The observed bands with origins at 7192.34 and ∼7366 cm-1 are assigned to the symmetric acceptor OH-stretching first overtone and the OH-stretching combination of the donor, respectively.
AB - Intramolecular vibrational transition wavenumbers and intensities were calculated in the fundamental HOH-bending, fundamental OH-stretching, first OH-stretching-HOH-bending combination, and first OH-stretching overtone (ΔvOH = 2) regions of the water dimer's spectrum. Furthermore, the rotational-vibrational spectrum was calculated in the ΔvOH = 2 region at 10 K, corresponding to the temperature of the existing jet-expansion experiments. The calculated spectrum was obtained by combining results from a full-dimensional (12D) vibrational and a reduced-dimensional vibrational-rotational-tunneling model. The ΔvOH = 2 spectral region is rich in features due to contributions from multiple vibrational-rotational-tunneling sub-bands. Origins of the experimental vibrational bands depend on the assignment of the observed sub-bands. Based on our calculations, we assign the observed sub-bands, and our reassignment leads to new values for the vibrational band origins of the free donor and antisymmetric acceptor OH-stretching first overtones of ∼7227 and ∼7238 cm-1, respectively. The observed bands with origins at 7192.34 and ∼7366 cm-1 are assigned to the symmetric acceptor OH-stretching first overtone and the OH-stretching combination of the donor, respectively.
U2 - 10.1021/acs.jpca.3c03705
DO - 10.1021/acs.jpca.3c03705
M3 - Journal article
C2 - 37930939
AN - SCOPUS:85177103447
VL - 127
SP - 9409
EP - 9418
JO - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
JF - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
SN - 1089-5639
IS - 45
ER -
ID: 374462515