Vibronic spectra of jet-cooled 2-Aminopurine · H2O clusters studied by UV resonant two-photon ionization spectroscopy and quantum chemical calculations

Rajeev K. Sinha, Simon Lobsiger, Maria Trachsel, Samuel Leutwyler

Research output: Contribution to journalArticle

17 Citations (Scopus)

Abstract

For understanding the major- and minor-groove hydration patterns of DNAs and RNAs, it is important to understand the local solvation of individual nucleobases at the molecular level. We have investigated the 2-aminopurine 3H2O monohydrate by two-color resonant two-photon ionization and UV/UV hole-burning spectroscopies, which reveal two isomers, denoted A and B. The electronic spectral shift δν of the S1←S 0 transition relative to bare 9H-2-aminopurine (9H-2AP) is small for isomer A (-70 cm-1), while that of isomer B is much larger (δν =-889 cm-1). B3LYP geometry optimizations with the TZVP basis set predict four cluster isomers, of which three are doubly H-bonded, with H2O acting as an acceptor to a N-H or -NH2 group and as a donor to either of the pyrimidine N sites. The "sugar-edge" isomer A is calculated to be the most stable form with binding energy De = 56.4 kJ/mol. Isomers B and C areH-bonded between the -NH2 group and pyrimidine moieties and are 2.5 and 6.9 kJ/mol less stable, respectively. Time-dependent (TD) B3LYP/TZVP calculations predict the adiabatic energies of the lowest 1ππ* states of A and B in excellent agreement with the observed 000 bands; also, the relative intensities of the A and B origin bands agree well with the calculated S0 state relative energies. This allows unequivocal identification of the isomers. The R2PI spectra of 9H-2AP and of isomer A exhibit intense low-frequency out-of-plane overtone and combination bands, which is interpreted as a coupling of the optically excited 1ππ* state to the lower-lying 1* dark state. In contrast, these overtone and combination bands are much weaker for isomer B, implying that the 1ππ* state of B is planar and decoupled from the 1* state. These observations agree with the calculations, which predict the 1* above the 1ππ* state for isomer B but below the 1ππ* for both 9H-2AP and isomer A.

Original languageEnglish
Pages (from-to)6208-6217
Number of pages10
JournalJournal of Physical Chemistry A
Volume115
Issue number23
DOIs
Publication statusPublished - 16-06-2011

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2-Aminopurine
Isomers
Ionization
Photons
isomers
Spectroscopy
ionization
photons
spectroscopy
pyrimidines
harmonics
Solvation
hole burning
sugars
Binding energy
Sugars
Hydration
grooves
solvation
hydration

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

Cite this

@article{1e51e1330096449a94e99de23fd9aec6,
title = "Vibronic spectra of jet-cooled 2-Aminopurine · H2O clusters studied by UV resonant two-photon ionization spectroscopy and quantum chemical calculations",
abstract = "For understanding the major- and minor-groove hydration patterns of DNAs and RNAs, it is important to understand the local solvation of individual nucleobases at the molecular level. We have investigated the 2-aminopurine 3H2O monohydrate by two-color resonant two-photon ionization and UV/UV hole-burning spectroscopies, which reveal two isomers, denoted A and B. The electronic spectral shift δν of the S1←S 0 transition relative to bare 9H-2-aminopurine (9H-2AP) is small for isomer A (-70 cm-1), while that of isomer B is much larger (δν =-889 cm-1). B3LYP geometry optimizations with the TZVP basis set predict four cluster isomers, of which three are doubly H-bonded, with H2O acting as an acceptor to a N-H or -NH2 group and as a donor to either of the pyrimidine N sites. The {"}sugar-edge{"} isomer A is calculated to be the most stable form with binding energy De = 56.4 kJ/mol. Isomers B and C areH-bonded between the -NH2 group and pyrimidine moieties and are 2.5 and 6.9 kJ/mol less stable, respectively. Time-dependent (TD) B3LYP/TZVP calculations predict the adiabatic energies of the lowest 1ππ* states of A and B in excellent agreement with the observed 000 bands; also, the relative intensities of the A and B origin bands agree well with the calculated S0 state relative energies. This allows unequivocal identification of the isomers. The R2PI spectra of 9H-2AP and of isomer A exhibit intense low-frequency out-of-plane overtone and combination bands, which is interpreted as a coupling of the optically excited 1ππ* state to the lower-lying 1nπ* dark state. In contrast, these overtone and combination bands are much weaker for isomer B, implying that the 1ππ* state of B is planar and decoupled from the 1nπ* state. These observations agree with the calculations, which predict the 1nπ* above the 1ππ* state for isomer B but below the 1ππ* for both 9H-2AP and isomer A.",
author = "Sinha, {Rajeev K.} and Simon Lobsiger and Maria Trachsel and Samuel Leutwyler",
year = "2011",
month = "6",
day = "16",
doi = "10.1021/jp111469n",
language = "English",
volume = "115",
pages = "6208--6217",
journal = "Journal of Physical Chemistry A",
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Vibronic spectra of jet-cooled 2-Aminopurine · H2O clusters studied by UV resonant two-photon ionization spectroscopy and quantum chemical calculations. / Sinha, Rajeev K.; Lobsiger, Simon; Trachsel, Maria; Leutwyler, Samuel.

In: Journal of Physical Chemistry A, Vol. 115, No. 23, 16.06.2011, p. 6208-6217.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Vibronic spectra of jet-cooled 2-Aminopurine · H2O clusters studied by UV resonant two-photon ionization spectroscopy and quantum chemical calculations

AU - Sinha, Rajeev K.

AU - Lobsiger, Simon

AU - Trachsel, Maria

AU - Leutwyler, Samuel

PY - 2011/6/16

Y1 - 2011/6/16

N2 - For understanding the major- and minor-groove hydration patterns of DNAs and RNAs, it is important to understand the local solvation of individual nucleobases at the molecular level. We have investigated the 2-aminopurine 3H2O monohydrate by two-color resonant two-photon ionization and UV/UV hole-burning spectroscopies, which reveal two isomers, denoted A and B. The electronic spectral shift δν of the S1←S 0 transition relative to bare 9H-2-aminopurine (9H-2AP) is small for isomer A (-70 cm-1), while that of isomer B is much larger (δν =-889 cm-1). B3LYP geometry optimizations with the TZVP basis set predict four cluster isomers, of which three are doubly H-bonded, with H2O acting as an acceptor to a N-H or -NH2 group and as a donor to either of the pyrimidine N sites. The "sugar-edge" isomer A is calculated to be the most stable form with binding energy De = 56.4 kJ/mol. Isomers B and C areH-bonded between the -NH2 group and pyrimidine moieties and are 2.5 and 6.9 kJ/mol less stable, respectively. Time-dependent (TD) B3LYP/TZVP calculations predict the adiabatic energies of the lowest 1ππ* states of A and B in excellent agreement with the observed 000 bands; also, the relative intensities of the A and B origin bands agree well with the calculated S0 state relative energies. This allows unequivocal identification of the isomers. The R2PI spectra of 9H-2AP and of isomer A exhibit intense low-frequency out-of-plane overtone and combination bands, which is interpreted as a coupling of the optically excited 1ππ* state to the lower-lying 1nπ* dark state. In contrast, these overtone and combination bands are much weaker for isomer B, implying that the 1ππ* state of B is planar and decoupled from the 1nπ* state. These observations agree with the calculations, which predict the 1nπ* above the 1ππ* state for isomer B but below the 1ππ* for both 9H-2AP and isomer A.

AB - For understanding the major- and minor-groove hydration patterns of DNAs and RNAs, it is important to understand the local solvation of individual nucleobases at the molecular level. We have investigated the 2-aminopurine 3H2O monohydrate by two-color resonant two-photon ionization and UV/UV hole-burning spectroscopies, which reveal two isomers, denoted A and B. The electronic spectral shift δν of the S1←S 0 transition relative to bare 9H-2-aminopurine (9H-2AP) is small for isomer A (-70 cm-1), while that of isomer B is much larger (δν =-889 cm-1). B3LYP geometry optimizations with the TZVP basis set predict four cluster isomers, of which three are doubly H-bonded, with H2O acting as an acceptor to a N-H or -NH2 group and as a donor to either of the pyrimidine N sites. The "sugar-edge" isomer A is calculated to be the most stable form with binding energy De = 56.4 kJ/mol. Isomers B and C areH-bonded between the -NH2 group and pyrimidine moieties and are 2.5 and 6.9 kJ/mol less stable, respectively. Time-dependent (TD) B3LYP/TZVP calculations predict the adiabatic energies of the lowest 1ππ* states of A and B in excellent agreement with the observed 000 bands; also, the relative intensities of the A and B origin bands agree well with the calculated S0 state relative energies. This allows unequivocal identification of the isomers. The R2PI spectra of 9H-2AP and of isomer A exhibit intense low-frequency out-of-plane overtone and combination bands, which is interpreted as a coupling of the optically excited 1ππ* state to the lower-lying 1nπ* dark state. In contrast, these overtone and combination bands are much weaker for isomer B, implying that the 1ππ* state of B is planar and decoupled from the 1nπ* state. These observations agree with the calculations, which predict the 1nπ* above the 1ππ* state for isomer B but below the 1ππ* for both 9H-2AP and isomer A.

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JO - Journal of Physical Chemistry A

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