Rovibrational matrix elements of the quadrupole moment of N 2 in a solid parahydrogen matrix

• Published in: The Journal of chemical physics 2008-11, Vol.129 (19), p.194503-194503-6
• Main Authors: Mishra, Adya P., Balasubramanian, T. K.
• Format: Article
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/1.3020712

The present work pertains to the study of the rotational dynamics of N 2 molecules solvated in a matrix of solid para- H 2 . It is shown that the mixing of the rotational states due to the anisotropic part of the N 2 - H 2 pair potential in the solid gives rise to an additional 5.4% contribution to the intensity of quadrupole-induced double transitions involving N 2 - H 2 pair. Hence the recently reported quadrupole moment matrix element of N 2 in a solid para- H 2 crystal [ A. P. Mishra and T. K. Balasubramanian , J. Chem. Phys. 125 , 124507 ( 2006 ) ], which was deduced from a comparison of the theoretical intensity (with rotational mixing of states neglected) with the measured value is larger by ∼ 2.7 % . The ground electronic state rovibrational matrix elements ⟨ v ′ J ′ | Q 2 ( r ) | v J ⟩ of N 2 molecule in a solid parahydrogen matrix for v , v ′ ≤ 1 and J , J ′ ≤ 4 have also been computed by taking into account the changes in the intramolecular potential of N 2 due to the intermolecular interaction in the matrix. The computed quadrupole moment matrix elements agree well with a few available values (for v = v ′ = 0 ) deduced from the observed transitions.