Theoretical density functional and ab initio computational study of the tautomeric, vibrational and H-bond properties of 1,7-di-CH3-guanine: A comparison with FT-IR data from matrix isolation experiments

J. Smets, K. Schoone, R. Ramaekers, Ludwik Adamowicz, G. Maes

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Abstract

In this work we report the results of a combined matrix-isolation FT-IR and theoretical computational DFT and ab initio study of the tautomeric and vibrational characteristics of 1,7-dimethyl-guanine (17DMG). The HF, MP2 and DFT methods are all in agreement in predicting that the amino-oxo tautomer of 17DMG is the most stable form, and that the imino-oxo tautomer, which can exist in two different geometrical isomers, is the second most stable form. The energy difference between the amino-oxo and amino-oxo tautomer is rather large: 23, 25 and 33 kJ mol-1, for the HF, DFT and MP2 methods, respectively. The imino-hydroxy tautomer is, according to the calculations, by far the least stable form (ΔE > 180 kJ mol-1). The FT-IR spectra of 17DMG isolated in an argon matrix are in agreement with the theoretical calculation indicating that only the amino-oxo tautomer should be present in the gas phase in detectable amounts. The experimental IR frequencies agree quite well with the theoretical values. When a single scaling factor is applied to approximately correct the calculated frequencies for various systematic errors in theoretical approach, the mean frequency deviations for the HF/6-31++G**, DFT /6-31G** and DFT/6-31++G** calculated spectra are 17.5 cm-1, 12.2 cm-1 and 16.3 cm-1, respectively. The DFT mean-frequency-deviations decrease to 8.1 cm-1 and 10.1 cm-1 when variable factors are applied. The stabilities of the different water complexes of the amino-oxo tautomer of 17DMG are investigated by optimizing the complexes at the HF/6-31++G** level of theory and calculating the MP2 energies at these optimized geometries. The N3...HO-H complex, which has a close structure with two H-bonds, is predicted to be the most stable structure. The MP2 calculated energy differences between the most stable complex and the C6=O...HO-H, the H-NH...OH2 and the H2N...HO-H hetero-dimers are 14.28 kJ mol-1, 1954 kJ mol-1 and 20.73 kJ mol-1, respectively.

Original languageEnglish (US)
Pages (from-to)201-220
Number of pages20
JournalJournal of Molecular Structure
Volume442
Issue number1-3
DOIs
StatePublished - Feb 3 1998

Fingerprint

guanines
tautomers
Guanine
Discrete Fourier transforms
isolation
matrices
Experiments
Argon
deviation
Gases
Systematic errors
systematic errors
Isomers
Dimers
energy
Water
isomers
dimers
argon
vapor phases

Keywords

  • Ab initio calculation
  • Density functional theory
  • Hydrogen bonding
  • Tautomerism
  • Vibration spectrum

ASJC Scopus subject areas

  • Structural Biology
  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Spectroscopy
  • Atomic and Molecular Physics, and Optics

Cite this

@article{2fce0d3a0f6f435996450aa86f19b038,
title = "Theoretical density functional and ab initio computational study of the tautomeric, vibrational and H-bond properties of 1,7-di-CH3-guanine: A comparison with FT-IR data from matrix isolation experiments",
abstract = "In this work we report the results of a combined matrix-isolation FT-IR and theoretical computational DFT and ab initio study of the tautomeric and vibrational characteristics of 1,7-dimethyl-guanine (17DMG). The HF, MP2 and DFT methods are all in agreement in predicting that the amino-oxo tautomer of 17DMG is the most stable form, and that the imino-oxo tautomer, which can exist in two different geometrical isomers, is the second most stable form. The energy difference between the amino-oxo and amino-oxo tautomer is rather large: 23, 25 and 33 kJ mol-1, for the HF, DFT and MP2 methods, respectively. The imino-hydroxy tautomer is, according to the calculations, by far the least stable form (ΔE > 180 kJ mol-1). The FT-IR spectra of 17DMG isolated in an argon matrix are in agreement with the theoretical calculation indicating that only the amino-oxo tautomer should be present in the gas phase in detectable amounts. The experimental IR frequencies agree quite well with the theoretical values. When a single scaling factor is applied to approximately correct the calculated frequencies for various systematic errors in theoretical approach, the mean frequency deviations for the HF/6-31++G**, DFT /6-31G** and DFT/6-31++G** calculated spectra are 17.5 cm-1, 12.2 cm-1 and 16.3 cm-1, respectively. The DFT mean-frequency-deviations decrease to 8.1 cm-1 and 10.1 cm-1 when variable factors are applied. The stabilities of the different water complexes of the amino-oxo tautomer of 17DMG are investigated by optimizing the complexes at the HF/6-31++G** level of theory and calculating the MP2 energies at these optimized geometries. The N3...HO-H complex, which has a close structure with two H-bonds, is predicted to be the most stable structure. The MP2 calculated energy differences between the most stable complex and the C6=O...HO-H, the H-NH...OH2 and the H2N...HO-H hetero-dimers are 14.28 kJ mol-1, 1954 kJ mol-1 and 20.73 kJ mol-1, respectively.",
keywords = "Ab initio calculation, Density functional theory, Hydrogen bonding, Tautomerism, Vibration spectrum",
author = "J. Smets and K. Schoone and R. Ramaekers and Ludwik Adamowicz and G. Maes",
year = "1998",
month = "2",
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doi = "10.1016/S0022-2860(97)00334-7",
language = "English (US)",
volume = "442",
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TY - JOUR

T1 - Theoretical density functional and ab initio computational study of the tautomeric, vibrational and H-bond properties of 1,7-di-CH3-guanine

T2 - A comparison with FT-IR data from matrix isolation experiments

AU - Smets, J.

AU - Schoone, K.

AU - Ramaekers, R.

AU - Adamowicz, Ludwik

AU - Maes, G.

PY - 1998/2/3

Y1 - 1998/2/3

N2 - In this work we report the results of a combined matrix-isolation FT-IR and theoretical computational DFT and ab initio study of the tautomeric and vibrational characteristics of 1,7-dimethyl-guanine (17DMG). The HF, MP2 and DFT methods are all in agreement in predicting that the amino-oxo tautomer of 17DMG is the most stable form, and that the imino-oxo tautomer, which can exist in two different geometrical isomers, is the second most stable form. The energy difference between the amino-oxo and amino-oxo tautomer is rather large: 23, 25 and 33 kJ mol-1, for the HF, DFT and MP2 methods, respectively. The imino-hydroxy tautomer is, according to the calculations, by far the least stable form (ΔE > 180 kJ mol-1). The FT-IR spectra of 17DMG isolated in an argon matrix are in agreement with the theoretical calculation indicating that only the amino-oxo tautomer should be present in the gas phase in detectable amounts. The experimental IR frequencies agree quite well with the theoretical values. When a single scaling factor is applied to approximately correct the calculated frequencies for various systematic errors in theoretical approach, the mean frequency deviations for the HF/6-31++G**, DFT /6-31G** and DFT/6-31++G** calculated spectra are 17.5 cm-1, 12.2 cm-1 and 16.3 cm-1, respectively. The DFT mean-frequency-deviations decrease to 8.1 cm-1 and 10.1 cm-1 when variable factors are applied. The stabilities of the different water complexes of the amino-oxo tautomer of 17DMG are investigated by optimizing the complexes at the HF/6-31++G** level of theory and calculating the MP2 energies at these optimized geometries. The N3...HO-H complex, which has a close structure with two H-bonds, is predicted to be the most stable structure. The MP2 calculated energy differences between the most stable complex and the C6=O...HO-H, the H-NH...OH2 and the H2N...HO-H hetero-dimers are 14.28 kJ mol-1, 1954 kJ mol-1 and 20.73 kJ mol-1, respectively.

AB - In this work we report the results of a combined matrix-isolation FT-IR and theoretical computational DFT and ab initio study of the tautomeric and vibrational characteristics of 1,7-dimethyl-guanine (17DMG). The HF, MP2 and DFT methods are all in agreement in predicting that the amino-oxo tautomer of 17DMG is the most stable form, and that the imino-oxo tautomer, which can exist in two different geometrical isomers, is the second most stable form. The energy difference between the amino-oxo and amino-oxo tautomer is rather large: 23, 25 and 33 kJ mol-1, for the HF, DFT and MP2 methods, respectively. The imino-hydroxy tautomer is, according to the calculations, by far the least stable form (ΔE > 180 kJ mol-1). The FT-IR spectra of 17DMG isolated in an argon matrix are in agreement with the theoretical calculation indicating that only the amino-oxo tautomer should be present in the gas phase in detectable amounts. The experimental IR frequencies agree quite well with the theoretical values. When a single scaling factor is applied to approximately correct the calculated frequencies for various systematic errors in theoretical approach, the mean frequency deviations for the HF/6-31++G**, DFT /6-31G** and DFT/6-31++G** calculated spectra are 17.5 cm-1, 12.2 cm-1 and 16.3 cm-1, respectively. The DFT mean-frequency-deviations decrease to 8.1 cm-1 and 10.1 cm-1 when variable factors are applied. The stabilities of the different water complexes of the amino-oxo tautomer of 17DMG are investigated by optimizing the complexes at the HF/6-31++G** level of theory and calculating the MP2 energies at these optimized geometries. The N3...HO-H complex, which has a close structure with two H-bonds, is predicted to be the most stable structure. The MP2 calculated energy differences between the most stable complex and the C6=O...HO-H, the H-NH...OH2 and the H2N...HO-H hetero-dimers are 14.28 kJ mol-1, 1954 kJ mol-1 and 20.73 kJ mol-1, respectively.

KW - Ab initio calculation

KW - Density functional theory

KW - Hydrogen bonding

KW - Tautomerism

KW - Vibration spectrum

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