Katsuhiko Okuyama

Vibronic coupling in the ground cationic state of naphthalene: A laser threshold photoelectron [zero kinetic energy (ZEKE)‐photoelectron] spectroscopic study

The two‐color (1+1’) threshold photoelectron spectra of naphthalene in a supersonic free jet have been recorded via nine vibronic levels of the S1 electronic state up to about 1420 cm−1 above the S1 band origin. The threshold photoelectron spectra recorded via the S1 band origin and via totally symmetric ag vibronic levels show significant intensity in Δν=+1 transitions in nontotally symmetric vibrations having b1g symmetry indicating that the ionization transition gains significant intensity through a vibronic coupling mechanism between the two lowest doublet cationic states. The strongest departure from the expected Δν=0 propensity in the threshold photoelectron spectra occurs through excitation of the totally symmetric 8 mode having ag symmetry indicating that a considerable displacement occurs along the normal coordinate of this 8 mode upon ionization from the S1 state. The superior resolution of the threshold photoelectron technique over conventional photoelectron methods has allowed accurate values for the fundamental vibrational frequencies of naphthalene in its ground cationic state to be determined and it has also allowed a more rigorous investigation of the vibronic coupling mechanism that occurs between the two lowest doublet cationic states. Moreover, an improved value for the adiabatic ionization energy of naphthalene of 65 687±7 cm−1 (8.1442±0.0009 eV) has been determined.The two‐color (1+1’) threshold photoelectron spectra of naphthalene in a supersonic free jet have been recorded via nine vibronic levels of the S1 electronic state up to about 1420 cm−1 above the S1 band origin. The threshold photoelectron spectra recorded via the S1 band origin and via totally symmetric ag vibronic levels show significant intensity in Δν=+1 transitions in nontotally symmetric vibrations having b1g symmetry indicating that the ionization transition gains significant intensity through a vibronic coupling mechanism between the two lowest doublet cationic states. The strongest departure from the expected Δν=0 propensity in the threshold photoelectron spectra occurs through excitation of the totally symmetric 8 mode having ag symmetry indicating that a considerable displacement occurs along the normal coordinate of this 8 mode upon ionization from the S1 state. The superior resolution of the threshold photoelectron technique over conventional photoelectron methods has allowed accurate values ...

Internal Rotation of the Methyl Group in the Electronically Excited State : o- and m-Toluidine

The fluorescence excitation and dispersed fluorescence spectra of jet-cooled o- and m-toluidine were observed. Vibrational analysis of the spectra provided us with the potentials for the internal rotation of the CH3 group in both ground and excited states. In o-toluidine, a large potential barrier to the internal rotation in the ground state is practically removed in the excited state. On the other hand, a nearly free internal rotation of the CH3 group in the ground state of m-toluidine gains a large barrier by the electronic excitation. The great change in the barrier height upon the electronic excitation is more remarkable than that found for fluorotoluene. A close relationship between the barrier height and the π electron density at the ring carbon atom was found, indicating the hyperconjugation as the origin of the barrier height in the absence of steric hindrance.

Electronic spectra of jet-cooled 1-phenylpyrrole: Large-amplitude torsional motion and twisted intramolecular charge-transfer phenomenon

The fluorescence excitation spectrum and the single vibronic level dispersed fluorescence spectra in the region of the S0⇆S1 transition were measured for jet-cooled 1-phenylpyrrole. The 0–0 band was observed at 35 493 cm−1. Long and low-frequency progressions with somewhat irregular intensity distributions appeared on both spectra, and were assigned to torsional motion. The torsional energy levels in the S0 and S1 states were obtained up to 25 and 16 quanta, respectively. The torsional potentials in both states could be determined from the sufficient number of energy levels observed. In the S0 state the most stable conformation was determined to be a twisted form with a dihedral angle of 38.7°, where the planar barrier height was calculated to be 457 cm−1, and the perpendicular to be 748 cm−1. On the other hand, it was discovered that 1-phenylpyrrole in the S1 state also had a twisted form with a somewhat smaller dihedral angle of 19.8°, and that the barrier to planarity was 105 cm−1 and to perpendiculari...

Laser threshold photoelectron spectra of the cis and trans rotational isomers of p-dimethoxybenzene-Arn (n=0,1,2) : observation of the intermolecular van der Waals stretching and bending vibrational modes in the cation

The cis and trans rotational isomers of p‐dimethoxybenzene–Arn (n=0,1,2) have been studied in a supersonic free jet by two‐color laser resonance enhanced multiphoton ionization threshold photoelectron spectroscopy. The two‐color (1+1’) threshold photoelectron spectra recorded via the S1 state of the cis and trans isomers of the 1:1 and 1:2 argon complexes reveal well resolved vibrational structure characteristic of the low frequency bending and stretching van der Waals vibrational modes. In the case of the trans isomer of the 1:2 complex, a very low frequency progression (11 cm−1) in a nontotally symmetric van der Waals bending mode appears in single quanta in the spectrum. The equivalent spectrum recorded for the cis isomer exhibits structure characteristic of van der Waals stretching modes as well as double quanta excitation in both totally symmetric and nontotally symmetric van der Waals bending modes. The observation of single quantum excitation in formally forbidden van der Waals vibrational modes im...

Observation of torsional motion in the ground-state cation of jet-cooled tolane by two-color threshold photoelectron spectroscopy

High‐resolution threshold photoelectron spectra of jet‐cooled tolane (C6H5–C≡C–C6H5) have been obtained by two‐color (1+1’) resonantly enhanced multiphoton ionization via the S1 state {1B1u(ππ*)}. From the threshold photoelectron spectra, the adiabatic ionization energy has been determined to be Ia = 63 917 ± 3 cm−1 (7.9243±0.0004 eV). A vibrational progression due to torsional motion in the cation ground state was observed up to its fifth quantum level with a fundamental frequency of 54 cm−1, showing small anharmonicity. From these results, we have evaluated the potential barrier height to the torsional motion to be 1980±60 cm−1. The threshold photoelectron spectra obtained via several S1 vibronic levels exhibit dominant peaks due to the Δv=0 ionization transitions. This fact indicates that no significant change occurs in molecular structure upon photoionization with removal of the antibonding π electron from the S1 state. Threshold photoelectron bands arising from formally forbidden odd quantum transiti...

REMPI threshold photoelectron spectra of the cis and trans rotational isomers of jet-cooled m-chlorophenol

Abstract The cis and trans rotational isomers of jet-cooled m -chlorophenol have been studied by two-colour (1+1′) laser threshold photoelectron spectroscopy. The adiabatic ionisation energy ( I a ) for each isomer was obtained from the positions of the respective zeroth vibrational peaks in the threshold photoelectron spectra. This yielded I a values of 8.655±0.001 eV for the cis isomer and 8.682±0.001 eV for the trans isomer. Additionally a provisional assignment of the vibrational structure observed in the ion current spectrum (S 1 state) and the threshold photoelectron spectra (D 0 state) has been made on the basis of comparison with the known ground state vibrational frequencies of the neutral molecule.

The role of electronic and geometric factors in ‘‘proton tunneling:’’ A comparative study of tropolone and 9‐hydroxyphenalenone by threshold photoelectron spectroscopy

High resolution two‐color threshold photoelectron spectra of tropolone and 9‐hydroxyphenalenone (9‐HPO) isolated in a free jet expansion have been measured to study the proton tunneling phenomena in the cation ground state (D0). The tunneling splitting widths of the D0 zeroth vibrational level for the both molecules lie within our experimental accuracy (2 cm−1), indicating that the proton tunneling is inhibited when compared to that obtained in their respective neutral states. By means of a comparative study of these two molecules, the tunneling inhibition has been explained in terms of a large contribution from the electronic factor which represents the changes in charge distribution of the π electrons upon ionization. The geometric factor, which is associated with the ring planarity is less important in determining the rate of tunneling in the D0 state. In the case of tropolone, we have found that the measurement of an out‐of‐plane skeletal vibration in various electronic states make it possible to desc...

Two-color threshold photoelectron spectroscopy: cation vibrational spectroscopy

Abstract We demonstrate that a capillary-type threshold photoelectron analyzer capable of an energy resolution of ±1–2 meV in two-color (1+1′) resonance ionization is a promising development in gas-phase cation vibrational spectroscopy, especially for studying low-frequency vibrational modes. The first example studied here is toluene. Several observed photoelectron vibrational bands due to the toluene cation show good correlation with our ab initio calculations. The second example studied is n -propylbenzene. The rotational isomers trans and gauche of the n -propylbenzene cat ion are clearly distinguished in our threshold photoelectron measurements. The trans and gauche isomers of this cation show quite different vibrational spectra in the low frequency region.

CH3 internal rotation in the S0 and S1 states of 9-methylanthracene.

Fluorescence excitation spectra and dispersed fluorescence spectra of jet-cooled 9-methylanthracene-h12 and -d12 (9MA-h12 and 9MA-d12) have been observed, and the energy levels of methyl internal rotation (CH3 torsion) in the S0 and S1 states have been analyzed. The molecular symmetry of 9MA is the same as that of toluene (G12). Because of two-fold symmetry in the pi system, the potential curve has six-fold barriers to CH3 rotation. In toluene, the barrier height to CH3 rotation V6 is very small, nearly free rotation. As for 9MA-h12, we could fit the level energies by potential curves with the barrier heights of V6(S0) = 118 cm(-1) and V6(S1) = 33 cm(-1). These barrier heights are remarkably larger than those of toluene and are attributed to hyperconjugation between the pi orbitals and methyl group. The dispersed fluorescence spectrum showed broad emission for the excitation of 0(0)(0) + 386 cm(-1) band, indicating that intramolecular vibrational redistribution efficiently occurs, even in the vibronic level of low excess energy of the isolated 9MA molecule.

S1-State Internal Conversion of Isolated Azulene Derivatives

The S0-S1 hole-burning spectra of azulene and its derivatives, 1-methyl, 2-methyl, 4-methyl, 1-cyano, and 2-cyanoazulenes, were measured under the isolated condition in order to gain an insight into the internal-conversion mechanism. The width of every 0-0 band was dependent on its transition energy and independent of the density of the S0-state vibrational levels isoenergetic to its zero level of the S1 state. On the contrary, the vibronic-band broadening of each molecule progressed in proportion to the vibrational excess energy of the S1 state. In the low-energy region, widths gradually increased, which is attributed to the normal internal conversion. A drastic increase was observed in the medium-energy region in azulene and three methyl derivatives but not in the two cyano ones. This is considered to be the onset of the relaxation process due to the conical intersection suggested by Bearpark et al. [J. Am. Chem. Soc. 1996, 118, 169]. Anomalous width behavior was found for two vibronic bands whose widths were still narrow even above the onset. One was 0 + 2659 cm(-1) band of azulene, that had been already reported by Ruth et al. [Phys. Chem. Chem. Phys. 1999, 1, 5121], and we could reproduce it by the hole-burning method. Another was 0 + 2878 cm(-1) band of 2-methylazulene. This is the vibronic selectivity in competition between the relaxation process and the normal internal conversion. The amplitude vectors of these modes were similar, including the in-plane bending of the CH bond and the stretching of the transannular bond.