Calculated rotational and vibrational g factors of LiH X ¹S⁺ and evaluation of parameters in radial functions from rotational and vibration-rotational spectra

TY - JOUR

T1 - Calculated rotational and vibrational g factors of LiH X 1S+ and evaluation of parameters in radial functions from rotational and vibration-rotational spectra

AU - Sauer, Stephan P. A.

AU - Paidarová, Ivana

AU - Oddershede, Jens

AU - Bak, Keld L.

AU - Ogilvie, John F.

PY - 2011/3/15

Y1 - 2011/3/15

N2 - The vibrational g factor, that is, the nonadiabatic correction to the vibrational reduced mass, of LiH has been calculated for internuclear distances over a wide range. Based on multiconfigurational wave functions with a large complete active space and an extended set of gaussian type basis functions, these calculations yielded also the rotational g factor, the electric dipolar moment, and its gradient with internuclear distance for LiH in its electronic ground state X 1∑+. The vibrational g factor g v exhibits a pronounced minimum near internuclear distance R = 3.65 × 10-10 m; the derivative of electric dipolar moment and the nonadiabatic matrix element coupling the electronic ground state to the first electronically excited state exhibit extrema near the same location that is also near the avoided crossing of the curves for potential energy for the electronic ground state and excited state A 1∑+. The irreducible contribution g rirr(R) to the rotational g factor increases monotonically over the calculated domain, whereas the irreducible contribution g virr(R) to the vibrational g factor has a minimum at the same location as that of gv itself. From these calculated radial functions, we derived values of the rotational g factor and electric dipolar moment for LiH in vibrational states v = 0 and 1, and the corresponding rotational dependences, in satisfactory agreement with experimental values. These calculated data of rotational g factor served as constraints in new fits of 1000 vibration-rotational spectral data of LiH in four isotopic variants, which yield estimates of adiabatic corrections for comparison with published data and of the vibrational g factor for comparison with our calculated results.

AB - The vibrational g factor, that is, the nonadiabatic correction to the vibrational reduced mass, of LiH has been calculated for internuclear distances over a wide range. Based on multiconfigurational wave functions with a large complete active space and an extended set of gaussian type basis functions, these calculations yielded also the rotational g factor, the electric dipolar moment, and its gradient with internuclear distance for LiH in its electronic ground state X 1∑+. The vibrational g factor g v exhibits a pronounced minimum near internuclear distance R = 3.65 × 10-10 m; the derivative of electric dipolar moment and the nonadiabatic matrix element coupling the electronic ground state to the first electronically excited state exhibit extrema near the same location that is also near the avoided crossing of the curves for potential energy for the electronic ground state and excited state A 1∑+. The irreducible contribution g rirr(R) to the rotational g factor increases monotonically over the calculated domain, whereas the irreducible contribution g virr(R) to the vibrational g factor has a minimum at the same location as that of gv itself. From these calculated radial functions, we derived values of the rotational g factor and electric dipolar moment for LiH in vibrational states v = 0 and 1, and the corresponding rotational dependences, in satisfactory agreement with experimental values. These calculated data of rotational g factor served as constraints in new fits of 1000 vibration-rotational spectral data of LiH in four isotopic variants, which yield estimates of adiabatic corrections for comparison with published data and of the vibrational g factor for comparison with our calculated results.

KW - Faculty of Science

KW - Quantum Chemistry

U2 - 10.1002/qua.22666

DO - 10.1002/qua.22666

M3 - Journal article

SN - 0020-7608

VL - 111

SP - 736

EP - 752

JO - International Journal of Quantum Chemistry

JF - International Journal of Quantum Chemistry

IS - 4

ER -