Anharmonic vibrational probe for N-methylacetamide in different micro-environments

被引：6

作者：

Cai, Kaicong ^{[1
]}

Liu, Diwen ^{[1
]}

Lou, Chenyu ^{[1
]}

Lin, Shen ^{[1
]}

机构：

[1] Fujian Normal Univ, Coll Chem & Chem Engn, Fuzhou 350007, Fujian, Peoples R China

来源：

VIBRATIONAL SPECTROSCOPY | 2013年 / 66卷

基金：

中国国家自然科学基金;

关键词：

Anharmonic vibrational frequency; DFT calculations; Amide I mode; Solvent effect; 2-DIMENSIONAL INFRARED-SPECTROSCOPY; 2D IR SPECTROSCOPY; AMIDE-I; LINE-SHAPES; PHOTON-ECHO; FREQUENCY; PEPTIDES; MODES; MAP; CONFORMATION;

D O I：

10.1016/j.vibspec.2013.01.005

中图分类号：

O65 [分析化学];

学科分类号：

070302 ; 081704 ;

摘要：

In the present study, anharmonic vibrational properties of the amide modes in N-methylacetamide (NMA), a model molecule for peptide vibrational spectroscopy, are examined by DFT calculations. The 3N-6 normal mode frequencies, diagonal and off-diagonal anharmonicities are evaluated by means of the second order vibrational perturbation theory (VPT2). Good performance of B3LYP/6-31+G** is found for predicting vibrational frequencies in comparison with gas phase experimental data. The amide vibrational modes are assigned through potential energy distribution analysis (PED). The solvation effect on the amide vibrational modes is modeled within the PCM method. From gas phase to polar solvents, red shifts are observed for both harmonic and anharmonic vibrational frequency of amide I mode while the C=O bond length increases upon the solvent polarity. Cubic and quartic force constants are further calculated to evaluate the origin of the anharmonicity for the amide I mode of NMA in different micro-environments. (C) 2013 Elsevier B.V. All rights reserved.

引用

页码：8 / 13

页数：6

共 55 条

[1] ON THE ABINITIO DETERMINATION OF HIGHER-ORDER FORCE-CONSTANTS AT NONSTATIONARY REFERENCE GEOMETRIES [J].

ALLEN, WD ;

CSASZAR, AG .

JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (04) :2983-3015

[2] THE PUCKERING INVERSION BARRIER AND VIBRATIONAL-SPECTRUM OF CYCLOPENTENE - A SCALED QUANTUM-MECHANICAL FORCE-FIELD ALGORITHM [J].

ALLEN, WD ;

CSASZAR, AG ;

HORNER, DA .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (17) :6834-6849

[3] Two-dimensional infrared spectroscopy of peptides by phase-controlled femtosecond vibrational photon echoes [J].

Asplund, MC ;

Zanni, MT ;

Hochstrasser, RM .

PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 2000, 97 (15) :8219-8224

[4] INFRARED STUDIES OF THE LESS STABLE CIS FORM OF N-METHYLFORMAMIDE AND N-METHYLACETAMIDE IN LOW-TEMPERATURE NITROGEN MATRICES AND VIBRATIONAL ANALYSES OF THE TRANS AND CIS FORMS OF THESE MOLECULES [J].

ATAKA, S ;

TAKEUCHI, H ;

TASUMI, M .

JOURNAL OF MOLECULAR STRUCTURE, 1984, 113 (MAR) :147-160

[5] Anharmonic vibrational properties by a fully automated second-order perturbative approach [J].

Barone, V .

JOURNAL OF CHEMICAL PHYSICS, 2005, 122 (01)

[6] Estimating the carbonyl anharmonic vibrational frequency from affordable harmonic frequency calculations [J].

Buczek, Aneta ;

Kupka, Teobald ;

Sauer, Stephan P. A. ;

Broda, Malgorzata A. .

JOURNAL OF MOLECULAR MODELING, 2012, 18 (06) :2471-2478

[7] Estimation of formamide harmonic and anharmonic modes in the Kohn-Sham limit using the polarization consistent basis sets [J].

Buczek, Aneta ;

Kupka, Teobald ;

Broda, Malgorzata A. .

JOURNAL OF MOLECULAR MODELING, 2011, 17 (09) :2265-2274

[8] Molecular mechanics force field-based map for peptide amide-I mode in solution and its application to alanine di- and tripeptides [J].

Cai, Kaicong ;

Han, Chen ;

Wang, Jianping .

PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2009, 11 (40) :9149-9159

[9] Multiple Anharmonic Vibrational Probes of Sugar Structure and Dynamics [J].

Cai, Kaicong ;

Wang, Jianping .

JOURNAL OF PHYSICAL CHEMISTRY B, 2009, 113 (06) :1681-1692

[10]

Califano S., 1976, VIBRATIONAL STATES

← 1 2 3 4 5 6 →