Vibrational spectra and static vibrational contribution to first hyperpolarizability of naphthopyrans - A combined experimental and DFT study

Kadali Chaitanya, Xue Hai Ju, B. Mark Heron, Christopher D. Gabbutt

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Abstract

Two pairs of isomeric photochromic naphthopyrans were investigated by FT-IR and FT-Raman spectroscopy and by density functional theory (DFT) methods. The vibrational frequencies and contribution to first hyperpolarizabilities of the four naphthopyrans were determined at the B3LYP/6-31G (d,p) level. Comparison of the experimental and theoretical vibrational frequencies of the naphthopyrans was made. The assignments of the vibrational spectra have been carried out with the help of normal co-ordinate analysis (NCA). These results show that the ratio between pure vibrational contribution to the electronic contribution of first hyperpolarizability (βv/βe) increases when the 4-methoxyphenyl groups in the symmetrical isomers is replaced by 4-morpholinophenyl and phenyl group resulting in an asymmetrically substituted isomer pair. At the static limit, the low vibrational frequency modes have dominating contributions to the vibrational dipole polarizability and first hyperpolarizability.

LanguageEnglish
Pages65-83
Number of pages19
JournalVibrational Spectroscopy
Volume69
Early online date21 Oct 2013
DOIs
Publication statusPublished - 18 Nov 2013
EventInternational Conference on Internet Computing - Las Vegas, United States
Duration: 23 Jun 200326 Jun 2003

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Vibrational spectra
Density functional theory
Isomers
Raman spectroscopy

Cite this

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title = "Vibrational spectra and static vibrational contribution to first hyperpolarizability of naphthopyrans - A combined experimental and DFT study",
abstract = "Two pairs of isomeric photochromic naphthopyrans were investigated by FT-IR and FT-Raman spectroscopy and by density functional theory (DFT) methods. The vibrational frequencies and contribution to first hyperpolarizabilities of the four naphthopyrans were determined at the B3LYP/6-31G (d,p) level. Comparison of the experimental and theoretical vibrational frequencies of the naphthopyrans was made. The assignments of the vibrational spectra have been carried out with the help of normal co-ordinate analysis (NCA). These results show that the ratio between pure vibrational contribution to the electronic contribution of first hyperpolarizability (βv/βe) increases when the 4-methoxyphenyl groups in the symmetrical isomers is replaced by 4-morpholinophenyl and phenyl group resulting in an asymmetrically substituted isomer pair. At the static limit, the low vibrational frequency modes have dominating contributions to the vibrational dipole polarizability and first hyperpolarizability.",
keywords = "FT-IR spectrum, Hyperpolarizabilities, Molecular geometry, Naphthopyran, Normal co-ordinate analysis, Raman spectrum",
author = "Kadali Chaitanya and Ju, {Xue Hai} and Heron, {B. Mark} and Gabbutt, {Christopher D.}",
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T1 - Vibrational spectra and static vibrational contribution to first hyperpolarizability of naphthopyrans - A combined experimental and DFT study

AU - Chaitanya, Kadali

AU - Ju, Xue Hai

AU - Heron, B. Mark

AU - Gabbutt, Christopher D.

PY - 2013/11/18

Y1 - 2013/11/18

N2 - Two pairs of isomeric photochromic naphthopyrans were investigated by FT-IR and FT-Raman spectroscopy and by density functional theory (DFT) methods. The vibrational frequencies and contribution to first hyperpolarizabilities of the four naphthopyrans were determined at the B3LYP/6-31G (d,p) level. Comparison of the experimental and theoretical vibrational frequencies of the naphthopyrans was made. The assignments of the vibrational spectra have been carried out with the help of normal co-ordinate analysis (NCA). These results show that the ratio between pure vibrational contribution to the electronic contribution of first hyperpolarizability (βv/βe) increases when the 4-methoxyphenyl groups in the symmetrical isomers is replaced by 4-morpholinophenyl and phenyl group resulting in an asymmetrically substituted isomer pair. At the static limit, the low vibrational frequency modes have dominating contributions to the vibrational dipole polarizability and first hyperpolarizability.

AB - Two pairs of isomeric photochromic naphthopyrans were investigated by FT-IR and FT-Raman spectroscopy and by density functional theory (DFT) methods. The vibrational frequencies and contribution to first hyperpolarizabilities of the four naphthopyrans were determined at the B3LYP/6-31G (d,p) level. Comparison of the experimental and theoretical vibrational frequencies of the naphthopyrans was made. The assignments of the vibrational spectra have been carried out with the help of normal co-ordinate analysis (NCA). These results show that the ratio between pure vibrational contribution to the electronic contribution of first hyperpolarizability (βv/βe) increases when the 4-methoxyphenyl groups in the symmetrical isomers is replaced by 4-morpholinophenyl and phenyl group resulting in an asymmetrically substituted isomer pair. At the static limit, the low vibrational frequency modes have dominating contributions to the vibrational dipole polarizability and first hyperpolarizability.

KW - FT-IR spectrum

KW - Hyperpolarizabilities

KW - Molecular geometry

KW - Naphthopyran

KW - Normal co-ordinate analysis

KW - Raman spectrum

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T2 - Vibrational Spectroscopy

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