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Keld L. Bak

Calculated Rotational and Vibrational g Factors of LiH X (1)Sigma(+) and Evaluation of Parameters in Radial Functions from Rotational and Vibration-Rotational Spectra

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Calculated Rotational and Vibrational g Factors of LiH X (1)Sigma(+) and Evaluation of Parameters in Radial Functions from Rotational and Vibration-Rotational Spectra. / Sauer, S. P. A.; Paidarová, I.; Oddershede, J.; Bak, Keld L.; Ogilvie, J. F.

In: International Journal of Quantum Chemistry, Vol. 111, No. 4, 15.03.2011, p. 736-752.

Research output: Contribution to journal/Conference contribution in journal/Contribution to newspaperJournal articleResearchpeer-review

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Sauer, SPA, Paidarová, I, Oddershede, J, Bak, KL & Ogilvie, JF 2011, 'Calculated Rotational and Vibrational g Factors of LiH X (1)Sigma(+) and Evaluation of Parameters in Radial Functions from Rotational and Vibration-Rotational Spectra', International Journal of Quantum Chemistry, vol. 111, no. 4, pp. 736-752. https://doi.org/10.1002/qua.22666

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Author

Sauer, S. P. A. ; Paidarová, I. ; Oddershede, J. ; Bak, Keld L. ; Ogilvie, J. F. / Calculated Rotational and Vibrational g Factors of LiH X (1)Sigma(+) and Evaluation of Parameters in Radial Functions from Rotational and Vibration-Rotational Spectra. In: International Journal of Quantum Chemistry. 2011 ; Vol. 111, No. 4. pp. 736-752.

Bibtex

@article{0f241bb220d44213bf8caca2244de6ac,
title = "Calculated Rotational and Vibrational g Factors of LiH X (1)Sigma(+) and Evaluation of Parameters in Radial Functions from Rotational and Vibration-Rotational Spectra",
abstract = "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)Sigma(+). The vibrational g factor g(v) exhibits a pronounced minimum near internuclear distance R = 3.65 x 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)Sigma(+). The irreducible contribution g(r)(irr)(R) to the rotational g factor increases monotonically over the calculated domain, whereas the irreducible contribution g(v)(irr)(R) to the vibrational g factor has a minimum at the same location as that of g(v) 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. (C) 2010 Wiley Periodicals, Inc. Int J Quantum Chem 111: 736-752, 2011",
keywords = "rotational g factor, vibrational g factor, nonadiabatic reduced mass, spectral fitting, LiH, BORN-OPPENHEIMER APPROXIMATION, ELECTRIC DIPOLAR MOMENT, DIATOMIC-MOLECULES, POTENTIAL-ENERGY, DUNHAM COEFFICIENTS, ANALYTIC TREATMENT, HYDROGEN HALIDES, LITHIUM HYDRIDE, G TENSORS, STATE",
author = "Sauer, {S. P. A.} and I. Paidarov{\'a} and J. Oddershede and Bak, {Keld L.} and Ogilvie, {J. F.}",
year = "2011",
month = "3",
day = "15",
doi = "10.1002/qua.22666",
language = "English",
volume = "111",
pages = "736--752",
journal = "International Journal of Quantum Chemistry",
issn = "0020-7608",
publisher = "JohnWiley & Sons, Inc.",
number = "4",

}

RIS

TY - JOUR

T1 - Calculated Rotational and Vibrational g Factors of LiH X (1)Sigma(+) and Evaluation of Parameters in Radial Functions from Rotational and Vibration-Rotational Spectra

AU - Sauer, S. P. A.

AU - Paidarová, I.

AU - Oddershede, J.

AU - Bak, Keld L.

AU - Ogilvie, J. 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)Sigma(+). The vibrational g factor g(v) exhibits a pronounced minimum near internuclear distance R = 3.65 x 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)Sigma(+). The irreducible contribution g(r)(irr)(R) to the rotational g factor increases monotonically over the calculated domain, whereas the irreducible contribution g(v)(irr)(R) to the vibrational g factor has a minimum at the same location as that of g(v) 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. (C) 2010 Wiley Periodicals, Inc. Int J Quantum Chem 111: 736-752, 2011

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)Sigma(+). The vibrational g factor g(v) exhibits a pronounced minimum near internuclear distance R = 3.65 x 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)Sigma(+). The irreducible contribution g(r)(irr)(R) to the rotational g factor increases monotonically over the calculated domain, whereas the irreducible contribution g(v)(irr)(R) to the vibrational g factor has a minimum at the same location as that of g(v) 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. (C) 2010 Wiley Periodicals, Inc. Int J Quantum Chem 111: 736-752, 2011

KW - rotational g factor

KW - vibrational g factor

KW - nonadiabatic reduced mass

KW - spectral fitting

KW - LiH

KW - BORN-OPPENHEIMER APPROXIMATION

KW - ELECTRIC DIPOLAR MOMENT

KW - DIATOMIC-MOLECULES

KW - POTENTIAL-ENERGY

KW - DUNHAM COEFFICIENTS

KW - ANALYTIC TREATMENT

KW - HYDROGEN HALIDES

KW - LITHIUM HYDRIDE

KW - G TENSORS

KW - STATE

U2 - 10.1002/qua.22666

DO - 10.1002/qua.22666

M3 - Journal article

VL - 111

SP - 736

EP - 752

JO - International Journal of Quantum Chemistry

JF - International Journal of Quantum Chemistry

SN - 0020-7608

IS - 4

ER -