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Title: An experimental and theoretical study on rotational constants of vibrationally excited CH 2 OO

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Grant/Contract Number:
FG02-05ER15694; 0220001104420
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Chemical Physics Letters
Additional Journal Information:
Journal Volume: 621; Journal Issue: C; Related Information: CHORUS Timestamp: 2017-05-10 09:09:03; Journal ID: ISSN 0009-2614
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Citation Formats

Nakajima, Masakazu, Yue, Qiang, Li, Jun, Guo, Hua, and Endo, Yasuki. An experimental and theoretical study on rotational constants of vibrationally excited CH 2 OO. Netherlands: N. p., 2015. Web. doi:10.1016/j.cplett.2014.12.039.
Nakajima, Masakazu, Yue, Qiang, Li, Jun, Guo, Hua, & Endo, Yasuki. An experimental and theoretical study on rotational constants of vibrationally excited CH 2 OO. Netherlands. doi:10.1016/j.cplett.2014.12.039.
Nakajima, Masakazu, Yue, Qiang, Li, Jun, Guo, Hua, and Endo, Yasuki. 2015. "An experimental and theoretical study on rotational constants of vibrationally excited CH 2 OO". Netherlands. doi:10.1016/j.cplett.2014.12.039.
title = {An experimental and theoretical study on rotational constants of vibrationally excited CH 2 OO},
author = {Nakajima, Masakazu and Yue, Qiang and Li, Jun and Guo, Hua and Endo, Yasuki},
abstractNote = {},
doi = {10.1016/j.cplett.2014.12.039},
journal = {Chemical Physics Letters},
number = C,
volume = 621,
place = {Netherlands},
year = 2015,
month = 2

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1016/j.cplett.2014.12.039

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Cited by: 11works
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  • We present a detailed investigation of the photodissociation of hydroxylamine following direct single-photon and vibrationally mediated two-photon excitation below 42thinsp000 cm{sup {minus}1}. In all cases the lowest dissociation channel [NH{sub 2}({tilde X}thinsp{sup 2}B{sub 1})+OH({tilde X}thinsp{sup 2}{Pi})] dominates. Single-photon dissociation at 240 nm releases most of the excess energy (20thinsp550 cm{sup {minus}1}) into relative translation (53{percent}) and NH{sub 2} internal energy (40{percent}, mostly vibrational). OH carries little internal energy (7{percent}), most of it in the form of rotational excitation. Torsional excitation during the dissociation step leads to rotational alignment of the OH fragments and a preferential population of the {Pi}(A{sup {double_prime}})more » component of the lambda doublet. Both are lost after isoenergetic two-photon excitation via O{endash}H stretching overtones of NH{sub 2}OH, also leading to higher internal excitation of the NH{sub 2} fragments ({approximately}50{percent}) at the expense of relative translation. At lower total excitation energies the relative translation takes up an increasing fraction of the total excess energy ({ge}80{percent} at 5820 cm{sup {minus}1} of excess energy). The results are discussed in terms of {ital ab initio} calculations using complete active space second-order perturbation theory with augmented triple-{zeta} basis sets for the lowest excited singlet states. One- and two-dimensional potential functions explain the OH product state distributions observed in different experiments in terms of the geometry relaxation of NH{sub 2}OH upon electronic excitation. Crossing between the lowest excitated A{sup {prime}} and A{sup {double_prime}} singlet states in the Franck{endash}Condon region leads to a barrier of {approximately}0.5 eV to dissociation in S{sub 1}, which dominates the photodissociation dynamics. {copyright} {ital 1999 American Institute of Physics.}« less
  • We report a photoelectron spectroscopy and computational study of two simple boron oxide species: BO– and BO2–. Vibrationally-resolved photoelectron spectra are obtained at several photon energies (355, 266, 193, and 157 nm) for the 10B isotopomers, 10BO– and 10BO2–. In the spectra of 10BO–, we observe transitions to the 2 sigma + ground state and the 2 pi excited state of 10BO at an excitation energy of 2.96 eV. The electron affinity of 10BO is measured to be 2.510 plus/minus 0.015 eV. The vibrational frequencies of the ground states of 10BO– and 10BO, and the 2 pi excited state aremore » measured to be 1,725 plus/minus 40, 1,935 30, and 1,320 plus/minus 40 cm-1, respectively. For 10BO2–, we observe transitions to the 2 pi g ground state and two excited states of 10BO2, 2 pi u and 2 signa u+, at excitation energies of 2.26 and 3.04 eV, respectively. The electron affinity of 10BO2 is measured to be 4.46 plus/minus 0.03 eV and the symmetrical stretching vibrational frequency of the 2 pi u excited state of 10BO2 is measured to be 980 plus/minus 30 cm-1. Both density functional and ab initio calculations are performed to elucidate the electronic structure and chemical bonding of the two boron oxide molecules. Comparisons with the isoelectronic AlO– and AlO2– species and the closely related molecules CO, N2, CN–, and CO2 are also discussed.« less
  • Raman Chirped Adiabatic Passage (RCAP) is an efficient method to climb the vibrational ladder of molecules. It was shown on the example of fixed-in-space HCl molecule that selective vibrational excitation can thus be achieved by RCAP and that population transfer can be followed by X-ray Photoelectron spectroscopy [S. Engin, N. Sisourat, P. Selles, R. Taïeb, and S. Carniato, Chem. Phys. Lett. 535, 192–195 (2012)]. Here, in a more detailed analysis of the process, we investigate the effects of highly excited electronic states and of molecular rotation on the efficiency of RCAP. Furthermore, we propose an alternative spectroscopic way to monitormore » the transfer by means of X-ray absorption spectra.« less
  • Dispersed fluorescence spectra from the CH[sub 2] [ital [tilde b]] [sup 1][ital B][sub 1][r arrow][ital [tilde a]] [sup 1][ital A][sub 1] band were recorded with time-resolution by Fourier transform emission spectroscopy after pulsed excitation of a single rotational level of the [ital [tilde b]] [sup 1][ital B][sub 1] (0,16[sup 0],0) state. Fluorescence observed from the initially excited level and from levels populated by rotational energy changing collisions with the bath gas (ketene) was used to deduce the state-to-state rate constants for rotational energy transfer and the state-resolved rate constants for total collisional removal of [ital [tilde b]] [sup 1][ital B][submore » 1] CH[sub 2]. The observed propensity rules for rotational energy transfer---[Delta][ital J]=[plus minus]2, [Delta][ital K][sub [ital a]]=0, and [Delta][ital K][sub [ital c]]=[plus minus]2---are consistent with a quadrupole--dipole interaction between [ital [tilde b]] [sup 1][ital B][sub 1] (0,16[sup 0],0) CH[sub 2] and ketene. The existence of a quadrupole in the intermolecular interaction suggests that the structure of CH[sub 2] in the [ital [tilde b]] [sup 1][ital B][sub 1] (0,16[sup 0],0) state, averaged over the time of a collision, must be linear. The state-to-state rotational energy transfer rate constants range from approximately equal to the hard sphere gas kinetic rate to four times the gas kinetic rate, with the largest rate constants between rotational levels with the smallest energy gaps. Examination of fluorescence spectra recorded with polarization analysis shows that rotationally elastic ([Delta][ital J]=0)[ital M] changing collisions are negligible.« less
  • The millimeter-wave rotational spectra of SiC-13 and vibrationally excited SiC in the X3Pi state have been measured between 149 and 291 GHz in a laboratory discharge through SiH4 and CO. Hyperfine splittings in the SiC-13 spectra are well resolved, allowing accurate determination of all four hyperfine constants. The fine-structure, rotational, centrifugal distortion, and lambda-doubling constants for SiC-13 and v = 1 SiC have been determined to sufficient accuracy that the entire rotational spectrum can be calculated into the far-IR. 15 refs.