Theoretical simulation of vibrational sum-frequency generation spectra from density functional theory: Application to p-nitrothiophenol and 2,4-dinitroaniline

J. Guthmuller, F. Cecchet, D. Lis, Y. Caudano, A.A. Mani, P.A. Thiry, A. Peremans, B. Champagne

Research output: Contribution to journalArticle

Abstract

The molecular orientation of adsorbed molecules forming selfassembled monolayers can be determined by combining vibrational sum-frequency generation (SFG) measurements with quantum chemical calculations. Herein, we present a theoretical methodology used to simulate the SFG spectra for different combinations of polarizations. These simulations are based on calculations of the IR vectors and Raman tensors, which are obtained from density functional theory computations. The dependency of the SFG vibrational signature with respect to the molecular orientation is presented for the molecules p-nitrothiophenol and 2,4-dinitroaniline. It is found that a suitable choice of basis set as well as of exchange-correlation (XC) functional is mandatory to correctly simulate the SFG intensities and consequently provide an accurate estimation of the adsor bed molecule orientation. Comparison with experimental data shows that calculations performed at the B3LYP/6-311 + + G(d,p) level of approximation provide good agreement with experimental frequencies, and with IR and Raman intensities. In particular, it is demonstrated that polarization and diffuse functions are compulsory for reproducing the IR and Raman spectra, and consequently vibrational SFG spectra, of systems such as p-nitrothiophenol. Moreover, the investigated XC functional reveal their influence on the relative intensities, which show rather systematic variations with the amount of Hartree-Fock exchange. Finally, further aspects of the modeling are revealed by considering the frequency dependence of the Raman tensors.
Original languageEnglish
Pages (from-to)2132-2142
Number of pages11
JournalChemPhysChem
Volume10
Issue number12
DOIs
Publication statusPublished - 24 Aug 2009

Fingerprint

Vibrational spectra
Density functional theory
density functional theory
Molecular orientation
Molecules
Tensors
simulation
Polarization
Raman scattering
Monolayers
tensors
molecules
polarization
2,4-dinitroaniline
beds
signatures
methodology
Raman spectra
approximation

Cite this

@article{4c51a2231b534aca9c547933a887f1fe,
title = "Theoretical simulation of vibrational sum-frequency generation spectra from density functional theory: Application to p-nitrothiophenol and 2,4-dinitroaniline",
abstract = "The molecular orientation of adsorbed molecules forming selfassembled monolayers can be determined by combining vibrational sum-frequency generation (SFG) measurements with quantum chemical calculations. Herein, we present a theoretical methodology used to simulate the SFG spectra for different combinations of polarizations. These simulations are based on calculations of the IR vectors and Raman tensors, which are obtained from density functional theory computations. The dependency of the SFG vibrational signature with respect to the molecular orientation is presented for the molecules p-nitrothiophenol and 2,4-dinitroaniline. It is found that a suitable choice of basis set as well as of exchange-correlation (XC) functional is mandatory to correctly simulate the SFG intensities and consequently provide an accurate estimation of the adsor bed molecule orientation. Comparison with experimental data shows that calculations performed at the B3LYP/6-311 + + G(d,p) level of approximation provide good agreement with experimental frequencies, and with IR and Raman intensities. In particular, it is demonstrated that polarization and diffuse functions are compulsory for reproducing the IR and Raman spectra, and consequently vibrational SFG spectra, of systems such as p-nitrothiophenol. Moreover, the investigated XC functional reveal their influence on the relative intensities, which show rather systematic variations with the amount of Hartree-Fock exchange. Finally, further aspects of the modeling are revealed by considering the frequency dependence of the Raman tensors.",
author = "J. Guthmuller and F. Cecchet and D. Lis and Y. Caudano and A.A. Mani and P.A. Thiry and A. Peremans and B. Champagne",
year = "2009",
month = "8",
day = "24",
doi = "10.1002/cphc.200900184",
language = "English",
volume = "10",
pages = "2132--2142",
journal = "ChemPhysChem",
issn = "1439-4235",
publisher = "Wiley-VCH Verlag",
number = "12",

}

Theoretical simulation of vibrational sum-frequency generation spectra from density functional theory : Application to p-nitrothiophenol and 2,4-dinitroaniline. / Guthmuller, J.; Cecchet, F.; Lis, D.; Caudano, Y.; Mani, A.A.; Thiry, P.A.; Peremans, A.; Champagne, B.

In: ChemPhysChem, Vol. 10, No. 12, 24.08.2009, p. 2132-2142.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Theoretical simulation of vibrational sum-frequency generation spectra from density functional theory

T2 - Application to p-nitrothiophenol and 2,4-dinitroaniline

AU - Guthmuller, J.

AU - Cecchet, F.

AU - Lis, D.

AU - Caudano, Y.

AU - Mani, A.A.

AU - Thiry, P.A.

AU - Peremans, A.

AU - Champagne, B.

PY - 2009/8/24

Y1 - 2009/8/24

N2 - The molecular orientation of adsorbed molecules forming selfassembled monolayers can be determined by combining vibrational sum-frequency generation (SFG) measurements with quantum chemical calculations. Herein, we present a theoretical methodology used to simulate the SFG spectra for different combinations of polarizations. These simulations are based on calculations of the IR vectors and Raman tensors, which are obtained from density functional theory computations. The dependency of the SFG vibrational signature with respect to the molecular orientation is presented for the molecules p-nitrothiophenol and 2,4-dinitroaniline. It is found that a suitable choice of basis set as well as of exchange-correlation (XC) functional is mandatory to correctly simulate the SFG intensities and consequently provide an accurate estimation of the adsor bed molecule orientation. Comparison with experimental data shows that calculations performed at the B3LYP/6-311 + + G(d,p) level of approximation provide good agreement with experimental frequencies, and with IR and Raman intensities. In particular, it is demonstrated that polarization and diffuse functions are compulsory for reproducing the IR and Raman spectra, and consequently vibrational SFG spectra, of systems such as p-nitrothiophenol. Moreover, the investigated XC functional reveal their influence on the relative intensities, which show rather systematic variations with the amount of Hartree-Fock exchange. Finally, further aspects of the modeling are revealed by considering the frequency dependence of the Raman tensors.

AB - The molecular orientation of adsorbed molecules forming selfassembled monolayers can be determined by combining vibrational sum-frequency generation (SFG) measurements with quantum chemical calculations. Herein, we present a theoretical methodology used to simulate the SFG spectra for different combinations of polarizations. These simulations are based on calculations of the IR vectors and Raman tensors, which are obtained from density functional theory computations. The dependency of the SFG vibrational signature with respect to the molecular orientation is presented for the molecules p-nitrothiophenol and 2,4-dinitroaniline. It is found that a suitable choice of basis set as well as of exchange-correlation (XC) functional is mandatory to correctly simulate the SFG intensities and consequently provide an accurate estimation of the adsor bed molecule orientation. Comparison with experimental data shows that calculations performed at the B3LYP/6-311 + + G(d,p) level of approximation provide good agreement with experimental frequencies, and with IR and Raman intensities. In particular, it is demonstrated that polarization and diffuse functions are compulsory for reproducing the IR and Raman spectra, and consequently vibrational SFG spectra, of systems such as p-nitrothiophenol. Moreover, the investigated XC functional reveal their influence on the relative intensities, which show rather systematic variations with the amount of Hartree-Fock exchange. Finally, further aspects of the modeling are revealed by considering the frequency dependence of the Raman tensors.

UR - http://www.scopus.com/inward/record.url?scp=68949161007&partnerID=8YFLogxK

U2 - 10.1002/cphc.200900184

DO - 10.1002/cphc.200900184

M3 - Article

AN - SCOPUS:68949161007

VL - 10

SP - 2132

EP - 2142

JO - ChemPhysChem

JF - ChemPhysChem

SN - 1439-4235

IS - 12

ER -