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Rotationally resolved photoelectron spectrum of the lowest singlet electronic state of NH2+ and ND2+: photoionization dynamics and rovibrational energy level structure of the state

Rotationally resolved photoelectron spectrum of the lowest singlet electronic state of NH2+ and ND2+: photoionization dynamics and rovibrational energy level structure of the state
Rotationally resolved photoelectron spectrum of the lowest singlet electronic state of NH2+ and ND2+: photoionization dynamics and rovibrational energy level structure of the state
Fully rotationally resolved pulsed-field-ionization zero-kinetic-energy photoelectron spectra of NH2 and ND2 have been recorded in the vicinity of the (X) over tilde B-2(1) --> (a) over tilde (+) (1)A(1) photoelectron band between 99 500 and 103 500 cm(-1). The spectra are dominated by a strong band attributed to the (X) over tilde B-2(1) (0, 0, 0) --> (a) over tilde+ (1)A(1) (0, 0, 0) transition. Weaker bands are assigned to transitions to highly excited bending levels of the (X) over tilde (+) B-3(1) ground ionic state and to the first symmetric stretching and bending levels of the (a) over tilde (+) state. The r(o) structure of the amidogen ion in its lowest singlet ((a) over tilde (+)) electronic state was derived from an analysis of the rotational structure (r(o)(N-H) = 1.051(3) Angstrom, alpha(o)(HNH) = 109.2(3)degrees). A model describing the rotational intensities in the photoelectron spectra of asymmetric top molecules [WILLITSCH, S., HOLLENSTEIN, U., and MERKT, F., 2004, J. chem. Phys., 120, 1761] was used to demonstrate that photoionization occurs out of a p orbital on the central N atom and that the photoelectron partial wave composition is dominated by the d component. No perturbations in the rotational structure of the lowest levels of the (a) over bar (+) state resulting from the Renner-Teller coupling to the (b) over tilde (+) state could be detected. The adiabatic ionization energy of the (X) over tilde --> (a) over tilde (+) transition was determined to be 100 305.8 +/- 0.8 cm(-1) (12.43633 +/- 0.000 10 eV) in NH2 and 100 366.2 +/- 0.9 cm(-1) (12.443 82 +/- 0.000 11 eV) in ND2.
absorption-spectrum, infrared-spectroscopy, triatomic-molecules, ionization-energy, quasi-linearity, methylene ch2, renner-teller, ground-state, intensity, systems
0026-8976
1543-1553
Willitsch, S.
d4f665c8-19fc-4dac-be5d-fae80e9fdce3
Dyke, J.M.
46393b45-6694-46f3-af20-d7369d26199f
Merkt, F.
9456079a-0bfd-4c05-8a3f-2d6218fc1a2b
Willitsch, S.
d4f665c8-19fc-4dac-be5d-fae80e9fdce3
Dyke, J.M.
46393b45-6694-46f3-af20-d7369d26199f
Merkt, F.
9456079a-0bfd-4c05-8a3f-2d6218fc1a2b

Willitsch, S., Dyke, J.M. and Merkt, F. (2004) Rotationally resolved photoelectron spectrum of the lowest singlet electronic state of NH2+ and ND2+: photoionization dynamics and rovibrational energy level structure of the state. Molecular Physics, 102 (14-15), 1543-1553. (doi:10.1080/00268970410001725855).

Record type: Article

Abstract

Fully rotationally resolved pulsed-field-ionization zero-kinetic-energy photoelectron spectra of NH2 and ND2 have been recorded in the vicinity of the (X) over tilde B-2(1) --> (a) over tilde (+) (1)A(1) photoelectron band between 99 500 and 103 500 cm(-1). The spectra are dominated by a strong band attributed to the (X) over tilde B-2(1) (0, 0, 0) --> (a) over tilde+ (1)A(1) (0, 0, 0) transition. Weaker bands are assigned to transitions to highly excited bending levels of the (X) over tilde (+) B-3(1) ground ionic state and to the first symmetric stretching and bending levels of the (a) over tilde (+) state. The r(o) structure of the amidogen ion in its lowest singlet ((a) over tilde (+)) electronic state was derived from an analysis of the rotational structure (r(o)(N-H) = 1.051(3) Angstrom, alpha(o)(HNH) = 109.2(3)degrees). A model describing the rotational intensities in the photoelectron spectra of asymmetric top molecules [WILLITSCH, S., HOLLENSTEIN, U., and MERKT, F., 2004, J. chem. Phys., 120, 1761] was used to demonstrate that photoionization occurs out of a p orbital on the central N atom and that the photoelectron partial wave composition is dominated by the d component. No perturbations in the rotational structure of the lowest levels of the (a) over bar (+) state resulting from the Renner-Teller coupling to the (b) over tilde (+) state could be detected. The adiabatic ionization energy of the (X) over tilde --> (a) over tilde (+) transition was determined to be 100 305.8 +/- 0.8 cm(-1) (12.43633 +/- 0.000 10 eV) in NH2 and 100 366.2 +/- 0.9 cm(-1) (12.443 82 +/- 0.000 11 eV) in ND2.

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More information

Published date: 2004
Additional Information: Special Issue: Eighteenth Colloquium on High Resolution Molecular Spectroscopy (Part I)
Keywords: absorption-spectrum, infrared-spectroscopy, triatomic-molecules, ionization-energy, quasi-linearity, methylene ch2, renner-teller, ground-state, intensity, systems

Identifiers

Local EPrints ID: 20340
URI: http://eprints.soton.ac.uk/id/eprint/20340
ISSN: 0026-8976
PURE UUID: b75936b7-9530-494e-b673-20c8b9adea24
ORCID for J.M. Dyke: ORCID iD orcid.org/0000-0002-9808-303X

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Date deposited: 16 Feb 2006
Last modified: 16 Mar 2024 02:36

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Contributors

Author: S. Willitsch
Author: J.M. Dyke ORCID iD
Author: F. Merkt

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