Dynamics and resonances of the H(2S) + CH+(X1Σ+) reaction in the electronic ground state: a detailed quantum wavepacket study.

Initial state-selected and energy resolved channel-specific reaction probabilities, integral cross sections and thermal rate constants of the H(2S) + CH+(X1Σ+) reaction are calculated within the coupled states approximation by a time-dependent wave packet propagation method. The new ab initio global potential energy surface (PES) of the electronic ground state (1 2A') of the system, recently reported by Li et al. [J. Chem. Phys., 2015, 142, 124302], is employed for this purpose. All partial wave contributions up to the total angular momentum J = 60 are considered to obtain the converged integral reaction cross section up to a collision energy of 1.0 eV. Thermal rate constants are calculated by averaging the reaction cross sections over the Boltzmann distribution of energies and compared with the available theoretical and experimental results for the temperature range 10-1000 K. Investigation of the channel-specific reaction attributes shows that the H abstraction (CH+ destruction) channel is highly favored over the H exchange channel. The effect of rotational and vibrational excitations of the CH+ reagent on the dynamics is also studied. The resonances formed during the course of the reaction are also identified by calculating the transition state spectrum and characterized in terms of the eigenfunctions and lifetimes. More than 260 vibrational levels are obtained and their eigenfunctions are calculated, which are represented in terms of the nodal assignments and the eigenenergies. They reveal both the local and hyperspherical behavior for the bound and quasibound states of the CH2+ complex in the ground 1 2A' surface. The lifetime analysis of the quasibound states indicates that the CH2+ resonances survive for as long as ∼400 fs at high energies (E ∼ 2.0 eV) and are expected to decay faster with further increasing energy. Finally, the type of mechanism for the formation of the product (C+ + H2) is elucidated.

Crystal structure of ethyl 2-(3,5-di-fluoro-phen-yl)quinoline-4-carboxyl-ate.

In the title compound, C18H13F2NO2, the two rings of the quinoline system are fused almost coaxially, with a dihedral angle between their planes of 2.28 (8)°. The plane of the attached benzene ring is inclined to the plane of the quinoline system by 7.65 (7)°. The carboxyl-ate group attached to the quinoline system is in an anti-periplanar conformation. There is a short intra-molecular C-H⋯O contact involving the carbonyl group. In the crystal, mol-ecules are linked via C-H⋯O hydrogen bonds, forming chains lying in the (1-10) plane.

1-[6-(1H-Indol-1-yl)pyridin-2-yl]-1H-indole-3-carbaldehyde.

In the title compound, C22H15N3O, the dihedral angle between the two indole units is 33.72 (3)°. The mol-ecular structure features a weak intra-molecular C-H⋯N inter-action. In the crystal, weak C-H⋯O and C-H⋯π inter-actions, forming a two-dimensional network parallel to the bc plane.

(E)-1-[2-(2-Nitro-styr-yl)-1-phenyl-sulfonyl-1H-indol-3-yl]propan-1-one.

In the title compound, C25H20N2O5S, the phenyl ring makes dihedral angles of 89.88 (8) and 13.98 (8)°, respectively, with the indole ring system and the nitro-benzene ring. The dihedral angle between the indole ring system and the nitro-benzene ring is 88.48 (11)°. The mol-ecular structure is stabilized by a weak intra-molecular C-H⋯O inter-action. In the crystal, π-π inter-actions, with centroid-centroid distances of 3.6741 (18) and 3.8873 (17) Å, link the mol-ecules into layers parallel to the ab plane.

(E)-2-Bromo-1-[2-(2-nitro-styr-yl)-1-phenyl-sulfonyl-1H-indol-3-yl]ethanone.

In the title compound C24H17BrN2O5S, the phenyl ring makes dihedral angles of 85.4 (2) and 8.8 (2)° with the indole ring system and the nitro-benzene ring, respectively, while the indole ring system and nitrobenzene ring make a dihedral angle of 80.1 (2)°. In the crystal, weak C-H⋯O inter-actions link the mol-ecules, forming a two-dimensional network parallel to the bc plane.

9-[4-(Azido-meth-yl)phen-yl]-9H-carbazole-3-carbo-nitrile.

In the title compound C20H13N5, the dihedral angle between the carbazole ring system (r.m.s. deviation = 0.027 Å) and the pendant benzene ring is 55.08 (6)°. One of the azide N atoms is disordered over two positions in a 0.65 (2):0.35 (2) ratio. In the crystal, aromatic π-π stacking is observed [minimum centroid-centroid separation = 3.6499 (13) Å] as well as inversion-dimers connected by pairs of weak C-H⋯π inter-actions.

2-Bromo-1-(1-phenyl-sulfonyl-1H-indol-3-yl)propan-1-one.

In the title compound, C17H14BrNO3S, the phenyl ring makes a dihedral angle of 89.78 (16)° with the plane of the indole ring system. The terminal Br atom and the methyl group are disordered over two sets of sites, with site occupancies of 0.860 (2) and 0.140 (2). In the crystal, mol-ecules are linked into a chain along the b-axis direction by weak C-H⋯O hydrogen bonds. The chains are further linked by C-H⋯π inter-actions, forming layers parallel to the bc plane.

(Naphthalen-1-yl){2-[(5,6,7,8-tetrahydronaphthalen-2-yl)carbonyl]phenyl}methanone.

The title compound C28H22O2, basically consists of three ring systems, viz. a central benzene ring, with a lateral napthalene group to which it subtends a dihedral angle of 66.56 (4)° and a tetra-hydro-pyran ring exhibiting a half-chair conformation. The mol-ecular structure is stabilized by a weak intra-molecular C-H⋯O inter-action, while the crystal packing features weak C-H⋯π contacts.

(E)-2-[(2-Formyl-phen-oxy)meth-yl]-3-(4-iso-propyl-phen-yl)acrylo-nitrile.

In the title compound, C20H19NO2, the dihedral angle between the benzene rings is 77.12 (8)°. The terminal isopropyl group is disordered over two orientations, with site occupancies of 0.720 (14) and 0.280 (14). In the crystal, mol-ecules are linked through a weak C-H⋯O inter-action, forming a zigzag chain along the c-axis direction.

8-Bromo-3-(4-ethyl-phen-yl)-1-phenyl-3,3a,4,9b-tetra-hydro-1H-chromeno[4,3-c]isoxazole-3a-carbo-nitrile.

In the title compound, C25H21BrN2O2, the fused isoxazolidine ring adopts an envelope conformation with the N atom at the flap and the mean plane of the ring makes dihedral angles of 54.37 (12) and 87.32 (13)°, respectively, with the adjacent phenyl and benzene rings. The tetra-hydro-pyran ring has a half-chair conformation. In the crystal, mol-ecules are linked into a double-column structure along the b-axis direction through weak C-H⋯O and C-H⋯π inter-actions.

Methyl 11,14,16-triphenyl-8,12-dioxa-14,15-di-aza-tetra-cyclo-[8.7.0.0(2,7).0(13,17)]hepta-deca-2(7),3,5,13(17),15-penta-ene-10-carboxyl-ate.

In the title compound, C33H26N2O4, the pyrazole ring makes dihedral angles of 15.13 (7) and 60.80 (7)° with the adjacent phenyl rings. Both di-hydro-pyran rings exhibit half-chair conformations. A weak intra-molecular C-H⋯O inter-action occurs. In the crystal, mol-ecules are linked into inversion dimers through pairs of C-H⋯N inter-actions. Weak C-H⋯π inter-actions are also observed.

Di-µ-hydroxido-κ(4) O:O-di-µ-perchlorato-κ(4) O:O'-bis-[(2,2'-bi-pyridine-κ(2) N,N')copper(II)].

In the title binuclear copper(II) complex, [Cu2(ClO4)2(OH)2(C10H8N2)2], the Cu(II) ion is coordinated in the form of a Jahn-Teller distorted octahedron by two bi-pyridine N atoms, two perchlorate O atoms and two hydroxide O atoms, and displays a distorted octa-hedral geometry. The mol-ecule belongs to the symmetry point group C 2h . The Cu(II) ion is located on a twofold rotation axis and the hydroxide and perchlorate ligands are located on a mirror plane. Within the dinuclear mol-ecule, the Cu⋯Cu separation is 2.8614 (7) Å. The crystal structure exhibits O-H⋯O, C-H⋯O and π-π [centroid-centroid distance = 3.5374 (13) Å] inter-actions.

(E)-2-Bromo-methyl-3-(o-tol-yl)acrylo-nitrile.

The title compound C11H10BrN, has an E conformation at the C=C bond of the acrylo-nitrile unit. The vinyl group makes a dihedral angle of 44.53 (12)° with the benzene ring. In the crystal, weak C-H⋯π inter-actions involving the benzene ring are observed.

1,2-Bis(2-hy-droxy-5-methyl-benzyl-idene)hydrazine.

The mol-ecular structure of the title compound, C16H16N2O2, is stabilized by intra-molecular O-H⋯N hydrogen bonds with S(6) graph-set motifs, so that the mol-ecule is almost planar, with a C=N-N=C torsion angle of -179.7 (2)° and a dihedral angle of 1.82 (12)° between the aromatic rings. In the crystal, weak C-H⋯π inter-actions lead to the formation of a three-dimensional network.

6-Chloro-2-(4-meth-oxy-phen-yl)-4-phenyl-quinoline.

In the title compound, C22H16ClNO, the quinoline ring system makes dihedral angles of 56.30 (6) and 7.93 (6)°, respectively, with the adjacent phenyl and benzene rings. The dihedral angle between these phenyl and benzene rings is 56.97 (8)°. In the crystal, weak C-H⋯π and π-π [centroid-centroid distances of 3.7699 (9) and 3.8390 (9) Å] inter-actions link the mol-ecules into a layer parallel to the ab plane.

Dimethyl-ammonium 4-hy-droxy-benzoate.

In the crystal structure of the title compound, C(2)H(8)N(+)·C(7)H(5)O(3) (-), the anions and cations are linked by O-H⋯O and N-H⋯O hydrogen bonds into layers parallel to the ac plane.

N-[2-(3,4-Dimeth-oxy-phen-yl)eth-yl]-N-methyl-benzene-sulfonamide.

In the title compound, C(17)H(21)NO(4)S, the phenyl and dimeth-oxy-phenyl rings are almost perpendicular to each other, making a dihedral angle of 82.57 (5)°. The structure is stabilized by inter-molecular C-H⋯O inter-actions and the packing is further enhanced by C-H ⋯π inter-actions.

N-[2-(3,4-Dimeth-oxy-phenyl)eth-yl]-N-methyl-naphthalene-1-sulfonamide.

In the title compound, C(21)H(23)NO(4)S, the dihedral angle between the naphthalene residue and the benzene ring is 7.66 (3)°. In the molecule, there are some short C-H⋯O interactions. In the crystal, the structure is stabilized by weak intra-molecular C-H⋯O hydrogen bonds and the crystal structure is stabilized by weak C-H⋯O, C-H⋯π and π-π [centroid-centroid distance = 3.710 (2) Å] inter-actions.

2-Methyl-1-phenyl-sulfonyl-1H-indole-3-carbaldehyde.

In the title compound, C(16)H(13)NO(3)S, the sulfonyl-bound phenyl ring forms a dihedral angle of 84.17 (6)° with the indole ring system. An intra-molecular C-H⋯O hydrogen bond generates an S(6) ring motif. The crystal structure exhibits weak inter-molecular C-H⋯O hydrogen bonds and π-π inter-actions between the five- and six-membered rings of the indole group [centroid-centroid distance = 3.6871 (9) Å].

9-p-Tolyl-9H-carbazole-3-carbonitrile.

In the title compound, C(20)H(14)N(2), the carbazole ring system is essentially planar (r.m.s. deviation = 0.187 Å) and is inclined at an angle of 54.33 (4) ° with respect to the benzene ring. The crystal packing is stabilized by weak C-H⋯N and C-H⋯π inter-actions.