The optical rotatory power of water

Christine Isborn, Kacey Claborn, Bart Kahr

Research output: Contribution to journalArticle

Abstract

Ab initio molecular orbital calculations of the optical rotatory response of a single oriented water molecule are described. The unique tensor element gxy was computed to be -0.047 bohr3 with CCSD/6-311+G(d,p). A value of -0.033 was obtained with the minimal valence basis that was better suited to parsing the rotatory response among a limited number of excited states. Transition moments were calculated ab initio and qualitatively derived from the wave functions. Rotations were reckoned from the relative dispositions of the transition moments with respect to the wavevectors. In this way, it was possible to intuitively reckon the form of the optical rotation tensor consistent with that from higher levels of theory and to establish which excitations make the most significant contributions.

Original languageEnglish (US)
Pages (from-to)7800-7804
Number of pages5
JournalJournal of Physical Chemistry A
Volume111
Issue number32
DOIs
StatePublished - Aug 16 2007

Fingerprint

Tensors
tensors
Optical rotation
moments
Orbital calculations
Water
Molecular orbitals
Wave functions
Electron transitions
Excited states
water
excitation
molecular orbitals
wave functions
valence
Molecules
molecules

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

The optical rotatory power of water. / Isborn, Christine; Claborn, Kacey; Kahr, Bart.

In: Journal of Physical Chemistry A, Vol. 111, No. 32, 16.08.2007, p. 7800-7804.

Research output: Contribution to journalArticle

Isborn, Christine ; Claborn, Kacey ; Kahr, Bart. / The optical rotatory power of water. In: Journal of Physical Chemistry A. 2007 ; Vol. 111, No. 32. pp. 7800-7804.
@article{65b612e111e74ea3a910dfe8c2bdf0b1,
title = "The optical rotatory power of water",
abstract = "Ab initio molecular orbital calculations of the optical rotatory response of a single oriented water molecule are described. The unique tensor element gxy was computed to be -0.047 bohr3 with CCSD/6-311+G(d,p). A value of -0.033 was obtained with the minimal valence basis that was better suited to parsing the rotatory response among a limited number of excited states. Transition moments were calculated ab initio and qualitatively derived from the wave functions. Rotations were reckoned from the relative dispositions of the transition moments with respect to the wavevectors. In this way, it was possible to intuitively reckon the form of the optical rotation tensor consistent with that from higher levels of theory and to establish which excitations make the most significant contributions.",
author = "Christine Isborn and Kacey Claborn and Bart Kahr",
year = "2007",
month = "8",
day = "16",
doi = "10.1021/jp073439n",
language = "English (US)",
volume = "111",
pages = "7800--7804",
journal = "Journal of Physical Chemistry A",
issn = "1089-5639",
publisher = "American Chemical Society",
number = "32",

}

TY - JOUR

T1 - The optical rotatory power of water

AU - Isborn, Christine

AU - Claborn, Kacey

AU - Kahr, Bart

PY - 2007/8/16

Y1 - 2007/8/16

N2 - Ab initio molecular orbital calculations of the optical rotatory response of a single oriented water molecule are described. The unique tensor element gxy was computed to be -0.047 bohr3 with CCSD/6-311+G(d,p). A value of -0.033 was obtained with the minimal valence basis that was better suited to parsing the rotatory response among a limited number of excited states. Transition moments were calculated ab initio and qualitatively derived from the wave functions. Rotations were reckoned from the relative dispositions of the transition moments with respect to the wavevectors. In this way, it was possible to intuitively reckon the form of the optical rotation tensor consistent with that from higher levels of theory and to establish which excitations make the most significant contributions.

AB - Ab initio molecular orbital calculations of the optical rotatory response of a single oriented water molecule are described. The unique tensor element gxy was computed to be -0.047 bohr3 with CCSD/6-311+G(d,p). A value of -0.033 was obtained with the minimal valence basis that was better suited to parsing the rotatory response among a limited number of excited states. Transition moments were calculated ab initio and qualitatively derived from the wave functions. Rotations were reckoned from the relative dispositions of the transition moments with respect to the wavevectors. In this way, it was possible to intuitively reckon the form of the optical rotation tensor consistent with that from higher levels of theory and to establish which excitations make the most significant contributions.

UR - http://www.scopus.com/inward/record.url?scp=34548187238&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=34548187238&partnerID=8YFLogxK

U2 - 10.1021/jp073439n

DO - 10.1021/jp073439n

M3 - Article

VL - 111

SP - 7800

EP - 7804

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

SN - 1089-5639

IS - 32

ER -