Jeongmook Lee

Selective growth and field emission of vertically well-aligned carbon nanotubes on hole-patterned silicon substrates

We have achieved selective growth of high-purity carbon nanotubes (CNTs) on iron-deposited hole-patterns by thermal chemical vapor deposition (CVD) of acetylene gas. The vertically well-aligned CNTs were uniformly synthesized with good selectivity on hole-patterned silicon substrates. The CNTs indicated multiwalled and bamboo-like structure. The turn-on gate voltage at the CNT-based triode structure was about 55 V and emission current density was 2.0 μA at the applied gate voltage of 100 V.

State-selective predissociation dynamics of methylamines: The vibronic and H∕D effects on the conical intersection dynamics

The photodissociation dynamics of methylamines (CH(3)NH(2) and CD(3)ND(2)) on the first electronically excited state has been investigated using the velocity map ion imaging technique probing the H or D fragment. Two distinct velocity components are found in the H(D) translational energy distribution, implying the existence of two different reaction pathways for the bond dissociation. The high H(D) velocity component with the small internal energy of the radical fragment is ascribed to the N-H(D) fragmentation via the coupling of S(1) to the upper-lying S(2) repulsive potential energy surface along the N-H(D) bond elongation axis. Dissociation on the ground S(0) state prepared via the nonadiabatic dynamics at the conical intersection should be responsible for the slow H(D) fragment. Several S(1) vibronic states of methylamines including the zero-point level and nnu(9) states (n=1, 2, or 3) are exclusively chosen in order to explore the effect of the initial quantum content on the chemical reaction dynamics. The branching ratio of the fast and slow components is found to be sensitive to the initial vibronic state for the N-H bond dissociation of CH(3)NH(2), whereas it is little affected in the N-D dissociation event of CD(3)ND(2). The fast component is found to be more dominant in the translational distribution of D from CD(3)ND(2) than it is in that of H from CH(3)NH(2). The experimental result is discussed with a plausible mechanism of the conical intersection dynamics.

Conical intersection seam and bound resonances embedded in continuum observed in the photodissociation of thioanisole-d3

Herein, the multi-dimensional nature of the conical intersection seam has been experimentally revealed in the photodissociation reaction of thioanisole-d3 (C6H5SCD3) excited on S1, giving C6H5S·(Ã or X̃]) +·CD3 products. The translational energy distribution of the nascent·CD3 fragment, reflecting the relative yields of the C6H5S·(Ã) and C6H5S·(X̃) products, was measured at each S1 vibronic band using the velocity map ion imaging technique. Direct access of the reactant flux to the conical intersection seam leads to the increase of the nonadiabatic transition probability resulting in sharp resonances in the X̃/ÃC6H5S·product branching ratio at several distinct S1 vibronic bands. The nature of the S1 vibronic bands associated with such dynamic resonances was clarified by the mass-analyzed threshold ionization spectroscopy. The bound state embedded in continuum generated by the conical intersection is observed as a distinct dynamic resonance, revealing the nature of the nuclear motion responsible for the nonadiabatic coupling of two potential energy surfaces at the conical intersection. The multi-dimensional facets of the conical intersection seam in terms of its detailed structure and dynamic role are discussed with the aid of theoretical calculations.

Nuclear motion captured by the slow electron velocity imaging technique in the tunnelling predissociation of the S1 methylamine

Predissociation dynamics of methylamines (CH(3)NH(2) and CH(3)ND(2)) on the first electronically excited states are studied using the slow-electron velocity imaging method to unravel the multi-dimensional nature of the N-H(D) chemical bond dissociation reaction which occurs via tunnelling. The nearly free internal rotation around the C-N bond axis is found to be strongly coupled to the reaction pathway, revealing nuclear motions actively involved in the tunnelling process on the S(1) potential energy surfaces. The vibrational state-resolved energy and angular distributions of photoelectron, ejected from the ionization mediated by the metastable intermediate S(1) state provide a unique way for mapping the predissociative potential energy surfaces.

Structure and dynamic role of conical intersections in the πσ*-mediated photodissociation reactions

Conical intersection as a dynamic funnel in nonadiabatic transition dictates many important chemical reaction outputs such as reaction rates, yields, and energy disposals especially for chemical reactions taking place on electronically excited states. Therefore, the energetics and topology of conical intersections have been subjected to intensive theoretical and experimental studies for decades as these things are the keys to understanding and controlling nonadiabatic transitions which are ubiquitous in nature. In this article, we focus on πσ*-mediated photodissociation reactions of thiophenols and thioanisoles. Interestingly, for these chemical systems, the nonadiabatic transition probability can be precisely measured as a function of the excitation energy, giving a great opportunity for spectroscopic characterization of the multi-dimensional conical intersection seam that governs the nonadiabatic transition dynamics of polyatomic molecules. The passage of the reactive flux in the proximity of the conical intersection gives rise to dynamic resonances corresponding to dramatic state-specific increases of the nonadiabatic transition probability. Accordingly, it is found that the electronic and nuclear configurations of the reactive flux and their evolution, coupled to the conical intersection seam, are critical in nonadiabatic transition dynamics. Nonadiabaticity is found to be extremely sensitive to the conformational molecular structure, and this has been demonstrated in the photodissociation dynamics of the chemical derivatives of thiophenol. Intramolecular vibrational redistribution, which is nontrivial in surmounting the reaction barrier, is found to wash out state-specific dynamic resonances, implying the importance of the dynamic interplay between vibrational energy flow and nonadiabatic transition. The experimental results on conical intersection dynamics presented in this review provide many interesting and important issues to be pursued in the near future by both theoreticians and experimentalists.

Spectroscopic Separation of the Methyl Internal-Rotational Isomers of Thioanisole Isotopomers (C6H5S-CH2D and C6H5S-CHD2)

Two distinct rotational isomers of thioanisole-d1 (C6H5S-CH2D) and thioanisole-d2 (C6H5S-CHD2) with respect to the internal rotation of the methyl moiety have been identified and characterized spectroscopically using the resonantly enhanced two photon ionization, UV-UV hole burning, and slow-electron velocity map imaging techniques. From the statistical weights, the definite assignment for the specific rotational isomer of each isotopomer has been successfully done, providing isomer-specific ionization energies and vibrational frequencies of S1/D0 states. Detailed molecular structures, the methyl internal-rotor barrier, and normal-mode descriptions for selective vibrations are discussed with the aid of density functional theory calculations.

H/D substitution makes difference in photochemical studies: the case of dimethylamine

When the molecule in the excited state is subject to prompt predissociation, it is quite nontrivial to obtain vibrational structure of the excited state in general. This applies to the case of photochemistry of dimethylamine (DMA:(CH3)2NH). When DMA is excited to its first electronically excited state (S1), the N-H bond dissociation occurs promptly. Therefore, S1 vibronic bands are homogeneously broadened to give extremely small ionization cross sections and heavily-congested spectral features, making infeasible any reasonable spectral assignment. Here, we demonstrate that the predissociation rate of the excited state could be significantly reduced by the NH/ND substitution to give the much better-resolved S1 spectral feature, revealing the vibrational structure of the excited state of DMA-d1 ((CH3)2ND) for the first time.

Valence electron ionization dynamics of chromium by a photoelectron imaging technique: J+-dependent state and angular distribution.

The photoionization of Cr at excited states is investigated using a velocity-map photoelectron imaging technique. Benzene chromium carbonyl or bis(η(6)-benzene) chromium was used as a precursor for the generation of excited Cr atoms. The a (5)S2 → x (5)P°3 and a (5)D3 → y (5)D°2 transitions are then employed for the preparation of resonant intermediate states in a two-color two-photon ionization process, in which an electronic configurational change from 3d(4)((5)D)4s4p((1)P°) to 3d(4)4s((6)D(J+)) occurs. The photoelectron kinetic energy distribution is found to be very sensitive to the ionization energy and the total angular momentum quantum number of the chromium ion (J(+)). Anisotropy parameters associated with departing electrons also show significant variation depending on the energy and total angular momentum quantum number, suggesting that direct and/or indirect ionization should be quantum-mechanically mixed, manifesting the complicated nature of angular momentum couplings in the ionization continuum.