研究者詳細 - 菱川　明栄

論文 - 菱川　明栄

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Light-induced multiple electronic-state coupling of O-2(+) in intense laser fields 査読有り

A Hishikawa, SL Liu, A Iwasaki, K Yamanouchi

JOURNAL OF CHEMICAL PHYSICS 114 巻 ( 22 ) 頁： 9856 - 9862 2001年6月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：AMER INST PHYSICS

The dissociation processes, O-2(+)-->O++O, in intense laser fields (100 fs, similar to 3x10(14) W/cm(2)) are studied at the laser wavelength of 795 and 398 nm on the basis of the momentum imaging maps of the O+ fragment ions. The covariance map measurements are performed with high momentum resolution to assign securely the dissociation pathways. From the anisotropic momentum distribution of O+ with respect to the laser polarization direction, the electronic states of O-2(+) are found to be coupled exclusively through parallel transitions in the course of the dissociation process. The released kinetic energy of O+ for both 795 and 398 nm are interpreted consistently by a sequential coupling model of light-dressed potential curves of O-2(+) in the quartet Pi state manifold. (C) 2001 American Institute of Physics.

DOI： 10.1063/1.1368383

Ionization and fragmentation dynamics of benzene in intense laser fields by tandem mass spectroscopy 査読有り

R Itakura, J Watanabe, A Hishikawa, K Yamanouchi

JOURNAL OF CHEMICAL PHYSICS 114 巻 ( 13 ) 頁： 5598 - 5606 2001年4月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：AMER INST PHYSICS

Using a tandem time-of-flight mass spectrometer, benzene cations produced by the resonantly enhanced multiphoton ionization are mass separated and are exposed to intense laser fields (similar to 2x10(16) W/cm(2)) at lambda similar to 790 and 395 nm with the pulse duration of similar to 50 fs. Comparing the yields of the product ions with those obtained from neutral benzene molecules, the ionization and dissociation dynamics of benzene in intense laser fields is investigated. At lambda similar to 790 nm, the formation of parent benzene ions is a dominant process irrespective of the initial charge states, i.e., major products obtained when starting from neutral benzene are benzene cations and dications and those obtained when starting from benzene cation are benzene dications. On the other hand, at lambda similar to 395 nm, the fragmentation processes to produce C4Hi+(i=2-4) and C3Hj+(j=1-3) dominate over further ionization to the benzene dication for both cases starting from neutral benzene and benzene cation, indicating the population trapping occurs by the efficient confinement in the light-dressed mixture of the C and X states of benzene cations assisted by the ultrafast intramolecular decay process. (C) 2001 American Institute of Physics.

DOI： 10.1063/1.1352619

Resonance-state selective photodissociation of OCS (2(1)Sigma(+)): Rotational and vibrational distributions of CO fragments 査読有り

R Itakura, A Hishikawa, K Yamanouchi

JOURNAL OF CHEMICAL PHYSICS 113 巻 ( 16 ) 頁： 6598 - 6607 2000年10月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：AMER INST PHYSICS

The rotational and vibrational state distributions of the CO fragments produced through the photodissociation of OCS in the vacuum ultraviolet (VUV) region (150-155 nm), OCS (2 (1)Sigma (+))--> CO (X (1)Sigma (+))+S(S-1), are derived for the three lowest quasi-bound vibrational resonances (upsilon*=0-2) in the 2 (1)Sigma (+) state. The rotational state distributions of the CO fragments in the upsilon (CO)=0 and 1 vibrational states are determined, respectively, by the analysis of the rotational structures in the laser-induced fluorescence (LIF) spectra of the A(1)Pi -X (1)Sigma (+)(0,0) and (1,1) transitions of CO. The rotational temperatures of CO in the upsilon (CO)=0 state are low (similar to 100 K) for all the three resonances, while those in the upsilon (CO)=1 state are substantially higher, i.e., 2210, 940, and 810 K for upsilon*=0, 1, and 2, respectively. The vibrational state distributions of CO are derived from the Doppler spectroscopy of the counterpart S(S-1) fragments. From the analysis of the observed Doppler profiles, it is found for all the three lowest vibrational resonances of OCS that the vibrational distributions are represented well by the Boltzmann-type distribution with a vibrational temperature of around 7000 K. On the basis of these new findings, the energy partitioning in the photodissociation process through these three vibrational resonances in the 2 (1)Sigma (+) state is discussed. (C) 2000 American Institute of Physics. [S0021-9606(00)01740-2].

DOI： 10.1063/1.1310606

Extraction of molecular dynamics in intense laser fields from mass-resolved momentum imaging maps: application to Coulomb explosion of NO 査読有り

A Iwamae, A Hishikawa, K Yamanouchi

JOURNAL OF PHYSICS B-ATOMIC MOLECULAR AND OPTICAL PHYSICS 33 巻 ( 2 ) 頁： 223 - 240 2000年1月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：IOP PUBLISHING LTD

The nuclear dynamics of NO in intense laser fields (similar to 1.4 PW cm(-2)) is studied on the basis of the momentum-scaled time-of-flight spectra and mass-resolved momentum imaging maps of the atomic fragment ions, NP+ and Oq+ (p, q = 1-3), produced from the (p, q) Coulomb explosion pathways of NO, i.e. NO(p+q)+ --> Np+ + Oq+. A procedure to extract nuclear dynamics from the momentum maps is proposed by taking account of the effect of the finite detector size. The resultant nine (p, q) single-pathway components show that (a) the distributions of the N-O internuclear distance of NOz+ just before the Coulomb explosion exhibit significant broadening (similar to 1 Angstrom); (b) the distance at which the corresponding distribution takes a maximum increases from 1.68 to 2.34 Angstrom as z from 2 to 6 with a small amount of suppression at odd z (z = 3, 5); and (c) the atomic fragment ions exhibit narrower angular distributions for a larger total charge z (= p + q) of NOz+.

DOI： 10.1088/0953-4075/33/2/308

Ultrafast structural deformation of polyatomic molecules in intense laser fields 査読有り

K Yamanouchi, A Hishikawa, A Iwamae, SL Liu

PHYSICS OF ELECTRONIC AND ATOMIC COLLISIONS 500 巻頁： 182 - 191 2000年

記述言語：英語掲載種別：研究論文（国際会議プロシーディングス）出版者・発行元：AMER INST PHYSICS

The momentum vector distributions of fragment ions produced through the Coulomb explosion of small molecules such as NO, CO2, NO2, and H2O in intense laser fields (similar to 1 PW/cm(2)) are measured by the mass-resolved momentum imaging (MRMI) technique. For NO, the MRMI maps for a single (p,q) pathway, NO(p+q)+ --> NP+ + Oq+ (p, q = 1 similar to 3), are extracted from the observed MRMI maps on the basis of the momentum matching of the NP+ and Oq+. ion pair. In the MRMI maps for the fragment ions produced from CO2, NO2, and H2O, their ultrafast structural deformation both along the stretching coordinate and along the bending coordinate is identified. The <O-C-O angle distribution of CO2 Spreads significantly (FWHM similar to 40 degrees), and the <O-N-O bond angle of NO2 increases toward a linear configuration within the ultrashort duration of the laser pulse. This type of deformation is also identified for H2O. These structural deformations are most reasonably interpreted as a consequence of the formation of light-dressed potential energy surfaces.

Ultrafast structural deformation of NO2 in intense laser fields studied by mass-resolved momentum imaging 査読有り

A Hishikawa, A Iwamae, K Yamanouchi

JOURNAL OF CHEMICAL PHYSICS 111 巻 ( 19 ) 頁： 8871 - 8878 1999年11月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：AMER INST PHYSICS

The ultrafast structural deformation of NO2 in an intense laser field (1.0 PW/cm(2)) is studied by mass-resolved momentum imaging (MRMI) of the Op+ and Nq+ (p,q=1-3) fragment ions produced from NO2z+ through the Coulomb explosion processes, NO2z+--> Op++Nq++Or+ (z=p+q+r). The N-O distance just before the Coulomb explosion is elongated significantly from that in the electronic ground state, and it monotonically increases from 1.7 to 2.1 Angstrom as z increases from 4 to 9. The angle O-N-O bond angle increases toward a linear configuration as a function of z, which is interpreted in terms of the formation of the light-dressed potential energy surfaces. The two-body fragmentation pathways to produce NO+ and NO2+ are also investigated by the MRMI measurements to derive the extent of the asymmetrical bond elongation of one of the two N-O bonds. (C) 1999 American Institute of Physics. [S0021-9606(99)00443-2].

DOI： 10.1063/1.480233

Ultrafast deformation of the geometrical structure of CO2 induced in intense laser fields 査読有り

A Hishikawa, A Iwamae, K Yamanouchi

PHYSICAL REVIEW LETTERS 83 巻 ( 6 ) 頁： 1127 - 1130 1999年8月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：AMERICAN PHYSICAL SOC

Ultrafast deformation of geometrical structure of CO2 in an intense laser field (1.1 PW/cm(2) = 1.1 X 10(15) W/cm(2)) was investigated by momentum imaging of the fragment Op+ and Cq+ (p, q = 1-3) ions produced from CO2z+ through the Coulonnb explosion processes, CO2z+ --> Op+ + Cq+ + Or+ (z = p + q + r). The observed large mean amplitude along the angle O-C-O bond angle (similar to 40 degrees) was attributed to the ultrafast bending motion induced on the light-dressed potential energy surfaces.

DOI： 10.1103/PhysRevLett.83.1127

Vibrational propensity in the predissociation rate of SO2((C)over-tilde(1)B(2)) by two types of nodal patterns in vibrational wavefunctions 査読有り

T Sako, A Hishikawa, K Yamanouchi

CHEMICAL PHYSICS LETTERS 294 巻 ( 6 ) 頁： 571 - 578 1998年9月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：ELSEVIER SCIENCE BV

The absorption and laser-induced fluorescence spectra of the (C)over-tilde(1)B(2)-(X)over-tilde(1)A(1), band of SO2 were simultaneously measured between 221.5 and 208 nm under jet-cooled conditions. The fluorescence quantum yields above the dissociation threshold showed irregularity, reflecting a level specificity in the predissociation rate. The vibronic-level dependence in the predissociation rate was interpreted in terms of the nodal structure of the vibrational wavefunctions, constructed from a least-squares analysis of the observed vibrational energies in the C state. The vibrational wavefunctions can be categorized into two types of localized wavefunctions: one stretching along the dissociation coordinate which tends to afford a much faster dissociation rate than the other which folds perpendicularly to the dissociation coordinate. (C) 1998 Elsevier Science B.V. All rights reserved.

DOI： 10.1016/s0009-2614(98)00922-1

Coulomb explosion dynamics of N-2 in intense laser field by mass-resolved momentum imaging 査読有り

A Hishikawa, A Iwamae, K Hoshina, M Kono, K Yamanouchi

CHEMICAL PHYSICS 231 巻 ( 2-3 ) 頁： 315 - 329 1998年6月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：ELSEVIER SCIENCE BV

The Coulomb explosion reactions of N-2, N-2((p+q)+) --> Np+ + Nq+ caused by the irradiation of intense laser light (0.73-6.9 PW/cm(2)) were investigated by high-resolution time-of-flight (TOF) mass spectroscopy and by the mass-resolved two-dimensional momentum imaging (MRMI) method. Six explosion pathways(p, q) = (1, 1), (1,2), (1,3), (2, 2), (2, 3) and (3, 3) in addition to (0, 1), (0,2) dissociation pathways were identified, whose assignments were securely performed both from the momentum matching between the fragment pair and their correlation with the laser-field intensity dependence. The MRMI method, which visualizes the radial and angular momentum distributions of mass-selected fragment ions on a two-dimensional momentum plane, was used to correlate ion fragments produced after the Coulomb explosion. By examining theoretically synthesized MRMI maps, it was found that the momentum distributions of the fragment ions in a wide momentum range can be extracted by the MRMI technique. The relative yields of the explosion pathways at six different laser-field intensities were evaluated from the three-dimensional integration of the MRMI maps, and the intensity dependence of the formation of singly and multiply charged parent N-2((p+q) +) ions prior to the fragmentation was derived. (C) 1998 Elsevier Science B.V. All rights reserved.

DOI： 10.1016/S0301-0104(98)00025-1

Omega-type doubling reversal in the B-3 Pi(1) state of (HgAr)-Hg-200 as a probe of the long-range potential of the A(3)Pi(0)+ state 査読有り

A Hishikawa, H Sato, K Yamanouchi

JOURNAL OF CHEMICAL PHYSICS 108 巻 ( 22 ) 頁： 9202 - 9205 1998年6月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：AMER INST PHYSICS

The mass-resolved excitation spectrum of the B (II1)-I-3-X(1)Sigma(+) transition of HgAr was measured by the two-color resonantly enhanced two-photon ionization method using a high-resolution reflectron time-of-flight mass spectrometer. The rotational structures were recorded with high spectral resolution (similar to 0.05 cm(-1))for the (upsilon(B),0) bands (upsilon(B) = 0 - 9) of a single isotopomer (HgAr)-Hg-200. From the rotational analysis, the presence of an Omega-type doubling was identified for the first time, which is caused by the rotational perturbation from the nearby highly excited vibrational levels of the A (II0+)-I-3 state. The spacing between the Omega-type doublers was found to exhibit a characteristic reversal as a function of upsilon(B). From the deperturbation of the Omega-type doubling, the vibrational level energies of the A state in the vibrationally highly excited region were derived, from which its long-range interaction potential was determined. (C) 1998 American Institute of Physics. [S0021-9606(98)02822-0].

DOI： 10.1063/1.476415

Mass-resolved VUV laser spectroscopy of XeAr: Two competing predissociation pathways in the C1 state 査読有り

SL Liu, A Hishikawa, K Yamanouchi

JOURNAL OF CHEMICAL PHYSICS 108 巻 ( 13 ) 頁： 5330 - 5337 1998年4月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：AMER INST PHYSICS

Mass-resolved excitation spectra of the C1-X0(+) band of XeAr were measured under jet-cooled conditions using a tunable coherent vacuum ultraviolet (VUV) light (lambda similar to 130 nm) as an excitation light source and a high-resolution (m/Delta m similar to 1100) reflectron time-of-flight mass spectrometer. The rotational structure of the C1-X0(+) (upsilon',0) (upsilon'=2-6) vibronic bands were recorded by monitoring the parent (XeAr+)-Xe-132-Ar-40 ions and the fragment Xe-132(+) ions. From the analysis of the rotational structures, the existence of the two dissociation pathways from the C1 state was identified for the first time; i.e., (i) the rotationally dependent predissociation caused by an electron-rotation interaction (L- and/or S-uncoupling) with the dissociative state with 0(-) symmetry correlating with the Xe 6s'(1/2)(0) level, and (ii) the rotationally independent predissociation caused by the electrostatic interaction with a repulsive state with Omega = 1 symmetry correlated either with the Xe 6s(3/2)(1) level or the Xe 6s(3/2)(2) level. From the least-squares fit to the partially resolved rotational structures, the dissociation rates for these two pathways as well as the band origins and the rotational constants, were derived for the upsilon'=2-6 levels in the C1 state. (C) 1998 American Institute of Physics. [S0021-9606(98)01513-X].

DOI： 10.1063/1.475968

Rotational predissociation dynamics of H2O ((C)over-tilde(1)B(1)) by VUV laser-induced photofragment fluorescence spectroscopy 査読有り

SL Liu, A Hishikawa, K Yamanouchi

BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN 71 巻 ( 2 ) 頁： 355 - 362 1998年2月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：CHEMICAL SOC JAPAN

The rotational predissociation of water molecules in the vibrationless level of the (C) over tilde B-1(1) state was investigated under jet-cooled conditions (27-154 K) by exciting them with a tunable VUV laser in the wavelength range of 124.3-123.7 nm and by detecting the total fluorescence from electronically excited photofragments OH(A(2)Sigma (+)). Due to the simple one-photon selection rule and the efficient rotational cooling, individual low-J rotational transitions of the (C) over tilde B-1(1)-(X) over tilde (1)A(1) origin band were observed with almost no overlap in the laser-induced photofragment fluorescence (LIPF) spectrum. The widths and intensities of these rotational transitions exhibited pronounced dependence on the parent rotational levels in the (C) over tilde B-1(1) state. The least-squares analysis of the observed line-widths (FWHM) of the resolved rotational transitions, Gamma 's, showed that they are well described by the formula, Gamma = Gamma (0) + a(a)[J(a)'(2)], with optimized parameters Gamma (0) = 2.5(1) cm(-1) and a(a) = 0.63(1) cm(-1), indicating that (i) the homogeneous interaction couples the (C) over tilde B-1(1) state with the (A) over tilde B-1(1) state to form OH fragments in the electronically ground (2)Pi (i) state and (ii) the heterogeneous (a-axis orbital-rotation) interaction couples the (C) over tilde B-1(1) state with the (B) over tilde (1)A(1) state to form OH fragments in the electronically excited A(2)Sigma (+) state. By taking account of the rotational line-broadening effect, the least-squares analysis was also performed to fit the observed spectral intensities to derive the branching ratio of the OH(A(2)Sigma (+)) formation via the (B) over tilde (1)A(1) state of H2O. It was found that the OH(A(2)Sigma (+)) formation branching ratio can be expressed by an exponential form, exp(-gamma [J(a)'(2)]), which was proposed first by Hodgson et al. [Mol. Phys., 54, 351 (1985)], and reproduces well the observed rotational intensity pattern when gamma = 0.097(7). By using this branching ratio and the previous data for the absorption oscillator strength, the absolute cross section to yield OH(A(2)Sigma (+)) photofragments was obtained as a function of the excitation energy.

DOI： 10.1246/bcsj.71.355

Cross section for disalignment of excited neon atoms due to neon or helium atom collisions 査読有り

T Wakabayashi, A Yamamoto, T Yaneda, T Furutani, A Hishikawa, T Fujimoto

JOURNAL OF PHYSICS B-ATOMIC MOLECULAR AND OPTICAL PHYSICS 31 巻 ( 2 ) 頁： 341 - 359 1998年1月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：IOP PUBLISHING LTD

In a positive column plasma of glow discharge in neon the population of metastable atoms (2p(5)3s configuration) is substantial. Linearly polarized pulsed laser light excited these atoms to one of the 2p(5)3p configuration levels, and the direct fluorescence was observed with its polarized components resolved. From the temporal development of the intensities of these components, the disalignment (depolarization) rate due to atom (neon or helium) collisions was determined. From its atom-density (<3 x 10(23) m(-3)) dependence the rate coefficient was determined, and from the temperature (42-650 K) dependence of the rate coefficient, the disalignment collision cross section was estimated as a function of energy in the energy range of the order of 10 meV. The cross section of the 2p(2) (Paschen notation) atoms has positive dependence on energy, while that of the 2p(7) atoms has a negative dependence. The cross sections thus determined serve asa quantitative test of the molecular potentials to the order of 1 cm(-1).
In order to confirm that the temperature of the metastable atoms in the plasma is equal to the temperature of the surrounding wall, an additional experiment was performed; the line profile of the CW laser-induced fluorescence was observed for a plasma at liquid nitrogen temperature, and the metastable atom temperature was found to be 78 K.

DOI： 10.1088/0953-4075/31/2/015

Mass-resolved two-dimensional momentum imaging of the Coulomb explosion of N-2 and SO2 in an intense laser field 査読有り

A Hishikawa, A Iwamae, K Hoshina, M Kono, K Yamanouchi

CHEMICAL PHYSICS LETTERS 282 巻 ( 3-4 ) 頁： 283 - 291 1998年1月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：ELSEVIER SCIENCE BV

The Coulomb explosion reactions of N-2 and SO2 caused by the irradiation of intense laser light were investigated by high-resolution mass spectroscopy. For N-2, from the least-squares fit to the split mass patterns for the N+, N2+ and N3+ channels, kinetic energy releases of six explosion pathways were determined. By rotating the laser polarization direction with respect to the detection axis, angular distributions for the singly and multiply charged atomic ion fragments were obtained and were converted to mass-resolved two-dimensional momentum imaging (MRMI) maps. This MRMI method was found to be useful to correlate ion fragments produced after the Coulomb explosion. MRMI was also applied to the Coulomb explosion of SO2. (C) 1998 Elsevier Science B.V.

DOI： 10.1016/S0009-2614(97)01325-0

Coulomb explosion dynamics of N2O in intense laser-field: Identification of new two-body and three-body fragmentation pathways 査読有り

A Hishikawa, A Iwamae, K Hoshina, M Kono, K Yamanouchi

RESEARCH ON CHEMICAL INTERMEDIATES 24 巻 ( 7 ) 頁： 765 - 784 1998年

記述言語：英語出版者・発行元：VSP BV

The Coulomb explosion process of N2O in an intense laser-field (similar to 5 PW/cm(2)) has been investigated by the high-resolution time-of-flight (TOF) spectroscopy. Six two-body explosion pathways involving the NO+, NO2+, N-2(+) molecular ions have been securely identified from the momentum-scaled TOF spectra of the fragment ions. Assuming a linear geometry, three-body explosion pathways were investigated by sequential and concerted explosion models, When the concerted model is adopted, the observed momentum distributions of six atomic ion channels; N+, N2+, N3+, O+, O2+ and O3+, were well fitted using the Gaussian momentum distribution with the optimized bond elongation factor of 2.2(3). From the yields of individual Coulomb explosion pathways determined by the fit, the abundance of the parent ions, N2Oz+ (z = 2-8), prior to the two- body and three-body explosion processes was found to have a smooth distribution with a maximum at z similar to 3.

DOI： 10.1163/156856798x00401

Experimental and theoretical exploration of photodissociation of SO2 via the (C)over-tilde(1)B(2) state: identification of the dissociation pathway 査読有り

H Katagiri, T Sako, A Hishikawa, T Yazaki, K Onda, K Yamanouchi, K Yoshino

JOURNAL OF MOLECULAR STRUCTURE 413 巻頁： 589 - 614 1997年9月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：ELSEVIER SCIENCE BV

The photodissociation reaction of SO2 via the (C) over tilde(1)B(2) state, SO2 ((C) over tilde(1)B(2)) --> SO((3) Sigma(-)) + O(P-3) was investigated by experimental and theoretical approaches cooperatively to clarify its dissociation mechanism. We measured the laser induced fluorescence (LIF) spectrum of the (C) over tilde-(X) over tilde band in the short UV wavelength region (210-200 nm) under jet-cooled conditions. The fluorescence quantum yields and the dissociation rates of individual vibronic levels were determined in the 220-200-nm region using (i) the LIF spectrum measured in the present study, (ii) that measured previously by Yamanouchi et al. (J. Mol. Struct, 352/353 (1995) 541) in the longer wavelength region above 210 nm, and (iii) the high-resolution absorption spectrum measured by Freeman et al. (Planet. Space. Sci. 32 (1984) 1125). The dissociation rates were also derived in the 210-200-nm region from the broadening of the rotational lines of the (C) over tilde-(X) over tilde vibronic transitions. It was found that the dissociation rates determined through two different procedures were consistent with each other, and that the rate increases almost exponentially as an excess energy above the dissociation threshold increases though there is a certain fluctuation of the dissociation rates reflecting a mode specificity. We also performed theoretical ab initio calculations to derive potential energy surfaces (PESs) of the electronic ground states and low-lying electronically excited states of SO2 within the MCSCF and MRCI levels. The theoretical calculations showed that (i) the PES of the 2(1)A' state (the (C) over tilde(1)B(2) state in C-2r symmetry), correlating with the SO((1) Delta) + O(D-1) asymptote, crosses with the repulsive singlet (3(1)A') state, correlating with the SO((3) Sigma(-)) + O(P-3) asymptote, to form a pseudo-seam, (ii) the crossing pseudo-seam of these two PESs is located near the equilibrium bent angles for the X and C states along the energy contour of similar to 9700 cm(-1) measured from the SO((3) Sigma(-)) + O(P-3) dissociation limit, and (iii) the crossing seam between the 2(1)A' ((C) over tilde(1)B(2)) and repulsive 2(3)A' states is located in a lower energy region than the singlet seam; at similar to 6700 cm(-1) measured from the SO((3) Sigma(-)) + O(P-3) dissociation limit. On the basis of the above experimental and theoretical results together with the previous experimental evidence, we propose that (i) the photodissociation reaction via the (C) over tilde state proceeds mainly through the vibronic mixing between the (C) over tilde state vibronic levels with the quasi-bound dissociation continuum of the electronic ground X(1)A(1) state, and (ii) the additional dissociation channels may be open through the crossing seam with the repulsive singlet (3(1)A') state and that with the repulsive tiplet (2(3)A') slate in their narrow crossing energy regions. (C) 1997 Elsevier Science B.V.

DOI： 10.1016/S0022-2860(97)00199-3

PHOFEX spectroscopy of HgNe and HgAr: Determination of the dissociation energies of the X-1 Sigma(+), A(3)II(0)+, and (BII1)-I-3 states 査読有り

T Tasaka, K Onda, A Hishikawa, K Yamanouchi

BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN 70 巻 ( 5 ) 頁： 1039 - 1045 1997年5月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：CHEMICAL SOC JAPAN

Photofragment excitation (PHOFEX) spectroscopy was applied to determine the dissociation energies of the B-3 Pi(1) states of HgAr and HgNe. The PHOFEX spectra were measured in the wavelength region where the laser-induced fluorescence spectrum of the B-3 Pi(1)-X-1 Sigma(+) transition exhibits a continuum structure by probing the photolysis product of Hg(6(3)P(1)) through the Hg(8(3)S(1)-6(3)P(1)) transition. By the spectral simulation of the threshold behavior of the high-resolution (Delta v approximate to 0.08 cm(-1)) PHOFEX spectrum, the thresholds for the photodissociation reaction, HgRg --> Hg(6(3)P(1)) + Rg, were determined to be 39447.9(3) and 39536.0(5) cm(-1) for Rg = Ne and Ar, respectively. From these thresholds, the dissociation energies, D-0's, of the B-3 Pi(1) states of HgNe and HgAr were determined to be D-0(B-3 Pi(1); HgNe)= 9.8(3) and Do(B-3 pi(1); HgAr)= 61.8(5) cm(-1), respectively. This direct determination of the dissociation energies of the B-3 Pi(1) states led to a determination of the D-0's for the X-1 Sigma(+) and A(3) Pi(0+) states; D-0(X-1 Sigma(+); HgNe)= 35.6(3), D-0(X-1 Sigma(+); HgAr)= 123.7(5), D-0(A(3) Pi(0+); HgNe)= 68.7(3), and D-0(A(3) Pi(0+); HgAr)= 348.8(6) cm(-1) In addition, the (v',0) vibronic bands of the B-3 Pi(1)-X-1 Sigma(+) transition of HgAr were re-measured with high resolution for v' = 0-8. From the transition wavenumbers of these vibronic bands, the Morse potential parameters were determined with high precision as omega(e) = 11.94(3) cm(-1) and omega(e)x(e) = 0.594(3) cm(-1).

DOI： 10.1246/bcsj.70.1039

Radiative lifetime measurements of the B (2)Sigma(+) state of BaH by laser spectroscopy 査読有り

LE Berg, K Ekvall, A Hishikawa, S Kelly

PHYSICA SCRIPTA 55 巻 ( 3 ) 頁： 269 - 272 1997年3月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：ROYAL SWEDISH ACAD SCIENCES

By applying laser resonance methods in the near infrared wavelength region around 900 nm, a time-resolved experiment has been performed on the low lying B (2) Sigma(+) state of barium hydride. The radiative lifetime is shown to vary with the rotational quantum number due to perturbations between the low lying A' 2 Delta, A (2) Pi and B (2) Sigma(+) states. The following lifetime was obtained for the BaH molecule, where local perturbations are assumed to be negligible:
tau(B (2) Sigma(+)(upsilon' = 0, J = 5.5))= 125 +/- 2ns.

DOI： 10.1088/0031-8949/55/3/003

Femtosecond transition-state dynamics of dissociating OCS on the excited (1)Sigma(+) potential energy surface 査読有り

A Hishikawa, K Ohde, R Itakura, SL Liu, K Yamanouchi, K Yamashita

JOURNAL OF PHYSICAL CHEMISTRY A 101 巻 ( 4 ) 頁： 694 - 704 1997年1月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：AMER CHEMICAL SOC

Ultrafast photodissociation dynamics of OCS on the dissociative potential energy surface (PES) of the electronically excited (1) Sigma(+) state was investigated by photofragment excitation (PHOFEX) spectroscopy and time-dependent wavepacket calculations. The high-resolution PHOFEX spectrum of the entire (1) Sigma(+)-(1) Sigma(+) transition (63 300-69 350 cm(-1)) in the vacuum ultraviolet (vacuum UV) region was measured under jet-cooled conditions by using a tunable vacuum UV laser as an excitation light source and by monitoring the fragment S(S-1) atom. Due to sufficient vibrational and rotational cooling in a supersonic jet, a simple and distinct vibrational progression of the (1) Sigma(+)-(1) Sigma(+) band was recorded free from vibrational hot bands and the broadening by rotational structure. The autocorrelation function obtained from a Fourier transform of the PHOFEX spectra clearly exhibited recurrences with a period of 42 fs, corresponding to a period of the vibrational motion at the transition state along the direction perpendicular to the dissociation coordinate, This interpretation of the ultrafast motion in the transition-state region was supported by the wavepacket calculation on the ab initio PES obtained in the present study, which afforded a period of 48 fs for vibrational motion along the in-phase CO and CS stretching mode at the transition state on the ab initio PES. The distinct six peaks broadened due to the fast dissociation process were assigned to the transitions at the upsilon(TS) 0-5 levels, where upsilon(TS) represents a vibrational quantum number for the Feshbach resonances in the in-phase stretching mode at the transition state. For the upsilon(TS) = 0 peak, the narrowest width corresponding to the lifetime, tau(upsilon(TS)), of tau(0) = 133 fs was obtained. It was found that the dissociation lifetime first becomes shorter for a larger upsilon(TS), i.e., tau(1) = 44 fs and tau(2) = 27 fs, and then, the peak width becomes narrower for the higher vibrational states above upsilon(TS) = 2, with corresponding lifetimes of tau(3) = 47 fs and tau(4) = 44 fs. This deceleration of the dissociation rate for the larger upsilon(TS) states was interpreted as a result of trapping of a wave function in the in-phase stretching or the CO stretching vibrational motion suppressing the motion along the dissociation coordinate. All six main peaks in the PHOFEX spectra exhibited a characteristic asymmetric profile, originating from the interference between the zero-order discrete states for the in-phase stretching vibration at the transition state and the zero-order continuum states corresponding with the motion along the dissociation coordinate. In the main progression of the PHOFEX spectra, the reversal of the asymmetry direction was also observed. This q-reversal phenomenon was ascribed to the characteristic shape of the excited (1) Sigma(+) PES near the transition region which causes a phase shift in the wave functions in a narrow energy range.

DOI： 10.1021/jp962423m

Photodissociating small polyatomic molecules in the VUV region: Resonances in the (1)Sigma(+)-(1)Sigma(+) band of OCS 査読有り

K Yamanouchi, K Ohde, A Hishikawa, DM Neumark

CHEMICAL REACTIONS AND THEIR CONTROL ON THE FEMTOSECOND TIME SCALE XXTH SOLVAY CONFERENCE ON CHEMISTRY 101 巻頁： 789 - 797 1997年

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