TY - JOUR

T1 - The isotropic remnant of the CO2 near-fully depolarized Raman 23 overtone

AU - Chrysos, M.

AU - Verzhbitskiy, I. A.

AU - Rachet, F.

AU - Kouzov, A. P.

PY - 2011/3/14

Y1 - 2011/3/14

N2 - In a recent paper [M. Chrysos, I. A. Verzhbitskiy, F. Rachet, and A. P. Kouzov, J. Chem. Phys. 134, 044318 (2011)], we showed that, in CO2, the 2ν3 transition generates a Raman line spectrum that is 98 depolarized, a property in agreement with general symmetry rules. Here, we present an extensive analysis, experimental and theoretical, of the isotropic remnant of this overtone. The isotropic spectrum turned out to be 45 times less intense than its anisotropic counterpart and to have a moment that is 350 times smaller than the moment of the anisotropic spectrum, in excellent agreement with theoretical predictions. Once the measured intensity (along with other data exclusively experimental) was fed back into the formula of the moment, a value for the CO2 mean-polarizability asymmetric stretch derivative δ2ᾱ/δq3 2 was returned that matches the best ab initio prediction to better than 4%. Agreement, in order of magnitude, was found between the intensity reported herein and that reported in the sole prior study of this overtone [G. Tejeda, B. Maté, and S. Montero, J. Chem. Phys. 103, 568 (1995)].

AB - In a recent paper [M. Chrysos, I. A. Verzhbitskiy, F. Rachet, and A. P. Kouzov, J. Chem. Phys. 134, 044318 (2011)], we showed that, in CO2, the 2ν3 transition generates a Raman line spectrum that is 98 depolarized, a property in agreement with general symmetry rules. Here, we present an extensive analysis, experimental and theoretical, of the isotropic remnant of this overtone. The isotropic spectrum turned out to be 45 times less intense than its anisotropic counterpart and to have a moment that is 350 times smaller than the moment of the anisotropic spectrum, in excellent agreement with theoretical predictions. Once the measured intensity (along with other data exclusively experimental) was fed back into the formula of the moment, a value for the CO2 mean-polarizability asymmetric stretch derivative δ2ᾱ/δq3 2 was returned that matches the best ab initio prediction to better than 4%. Agreement, in order of magnitude, was found between the intensity reported herein and that reported in the sole prior study of this overtone [G. Tejeda, B. Maté, and S. Montero, J. Chem. Phys. 103, 568 (1995)].

UR - http://www.scopus.com/inward/record.url?scp=79952656787&partnerID=8YFLogxK

U2 - 10.1063/1.3557820

DO - 10.1063/1.3557820

M3 - Article

AN - SCOPUS:79952656787

VL - 134

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 10

M1 - 104310

ER -