Excited state photochemically driven surface formation of benzene from acetylene ices on Pluto and in the outer solar system.

NASA's New Horizons mission unveiled a diverse landscape of Pluto's surface with massive regions being neutral in color, while others like Cthulhu Macula range from golden-yellow to reddish comprising up to half of Pluto's carbon budget. Here, we demonstrate in laboratory experiments merged with electronic structure calculations that the photolysis of solid acetylene - the most abundant precipitate on Pluto's surface - by low energy ultraviolet photons efficiently synthesizes benzene and polycyclic aromatic hydrocarbons excited state photochemistry thus providing critical molecular building blocks for the colored surface material. Since low energy photons deliver doses to Pluto's surface exceeding those from cosmic rays by six orders of magnitude, these processes may significantly contribute to the coloration of Pluto's surface and of hydrocarbon-covered surfaces of Solar System bodies such as Triton in general.

Fragment-Based Ab Initio Molecular Dynamics Simulation for Combustion.

We develop a fragment-based ab initio molecular dynamics (FB-AIMD) method for efficient dynamics simulation of the combustion process. In this method, the intermolecular interactions are treated by a fragment-based many-body expansion in which three- or higher body interactions are neglected, while two-body interactions are computed if the distance between the two fragments is smaller than a cutoff value. The accuracy of the method was verified by comparing FB-AIMD calculated energies and atomic forces of several different systems with those obtained by standard full system quantum calculations.

Cyclopentadienyl radical formation from the reaction of excited nitrogen atoms with benzene: a theoretical study.

Ab initio CCSD(T)/CBS//ωB97X-D/6-311+G(d,p) calculations of the C6H6N potential energy surface were performed to investigate the reaction mechanism underlying the reaction of atomic nitrogen (2D) with benzene. Thereafter, Rice-Ramsperger-Kassel-Marcus (RRKM) calculations of reaction rate constants and product branching ratios were performed under single-collision conditions. The results revealed that the N(2D) + C6H6 reaction in the case of statistical behavior is expected to produce hydrogen cyanide plus a cyclopentadienyl radical (91.

ReacNetGenerator: an automatic reaction network generator for reactive molecular dynamics simulations.

Reactive molecular dynamics (MD) simulation makes it possible to study the reaction mechanism of complex reaction systems at the atomic level. However, the analysis of MD trajectories which contain thousands of species and reaction pathways has become a major obstacle to the application of reactive MD simulation in large-scale systems. Here, we report the development and application of the Reaction Network Generator (ReacNetGenerator) method.

Formation mechanism and spectroscopy of CH radicals in extreme environments: a theoretical study.

This study examined the reaction mechanisms of singlet (rhombic) and triplet (linear) C4 with acetylene by using accurate ab initio CCSD(T)/CBS//B3LYP/6-311G(d,p) calculations followed by a kinetic analysis of various reaction pathways and computations of relative product yields in combustion and planetary atmospheres. These calculations were combined with the Rice-Ramsperger-Kassel-Marcus (RRKM) calculations of reaction rate constants for predicting product-branching ratios, which depend on the collision energy under single-collision conditions. The results demonstrate that the initial reaction begins with the formation of an intermediate 3i2 with an entrance barrier of 3.

Infrared Spectra of the 1-Methylvinoxide Radical and Anion Isolated in Solid Argon.

The 1-methylvinoxy radical (1-MVO) is an important intermediate in the combustion and tropospheric reaction of OH. However, the vibrational structures of this species and its anionic form, 1-methylvinoxide anion (1-MVO), are not fully known. Thus, in this study, we obtained the infrared (IR) absorption spectra of 1-MVO and 1-MVO trapped in a solid Ar matrix.

Direct IR Absorption Spectra of Propargyl Cation Isolated in Solid Argon.

The direct infrared (IR) absorption spectra of propargyl cations were recorded. These cations were generated via the electron bombardment of a propyne/Ar matrix sample during matrix deposition. Secondary photolysis with selected ultraviolet (UV) light was used for grouping the observed bands of various products.

Formation and identification of borane radical anions isolated in solid argon.

The infrared (IR) spectrum of borane(3) anions (BH) isolated in solid Ar was recorded; two vibrational modes were observed at 2259.4 and 606.6 cm, which were assigned to the BH stretching (ν) and out-of-plane large-amplitude (ν) modes, respectively.

UV absorption spectrum of allene radical cations in solid argon.

Electron bombardment during deposition of an Ar matrix containing a small proportion of allene generated allene cations. Further irradiation of the matrix sample at 385 nm destroyed the allene cations and formed propyne cations in solid Ar. Both cations were identified according to previously reported IR absorption bands.

Direct infrared observation of hydrogen chloride anions in solid argon.

To facilitate direct spectroscopic observation of hydrogen chloride anions (HCl), electron bombardment of CHCl diluted in excess Ar during matrix deposition was used to generate this anion. Subsequent characterization were performed by IR spectroscopy and quantum chemical calculations. Moreover the band intensity of HCl decays slowly when the matrix sample is maintained in the dark for a prolonged time.

Parity-dependent hairpin configurations of repetitive DNA sequence promote slippage associated with DNA expansion.

Repetitive DNA sequences are ubiquitous in life, and changes in the number of repeats often have various physiological and pathological implications. DNA repeats are capable of interchanging between different noncanonical and canonical conformations in a dynamic fashion, causing configurational slippage that often leads to repeat expansion associated with neurological diseases. In this report, we used single-molecule spectroscopy together with biophysical analyses to demonstrate the parity-dependent hairpin structural polymorphism of TGGAA repeat DNA.

Identification of a Simplest Hypervalent Hydrogen Fluoride Anion in Solid Argon.

Hypervalent molecules are one of the exceptions to the octet rule. Bonding in most hypervalent molecules is well rationalized by the Rundle-Pimentel model (three-center four-electron bond), and high ionic bonding between the ligands and the central atom is essential for stabilizing hypervalent molecules. Here, we produced one of the simplest hypervalent anions, HF, which is known to deviate from the Rundle-Pimentel model, and identified its ro-vibrational features.

Photochemistry and infrared spectrum of single-bridged diborane(5) anion isolated in solid argon.

Three-center two-electron bonds are important for understanding electron-deficient molecules. To examine such a molecule, we produced a diborane(5) anion with a single-bridged structure upon electron bombardment during matrix deposition of Ar containing a small proportion of diborane(6). The diborane(5) anion was destroyed upon photolysis at 180, 220, 385, and 450 nm, but not at 532 nm.

Theoretical investigations of absorption and fluorescence spectra of protonated pyrene.

The equilibrium geometry and 75 vibrational normal-mode frequencies of the ground and first excited states of protonated pyrene isomers were calculated and characterized in the adiabatic representation by using the complete active space self-consistent field (CASSCF) method. Electronic absorption spectra of solid neon matrixes in the wavelength range 495-415 nm were determined by Maier et al. and they were analyzed using time-dependent density functional theory calculations (TDDFT).

Dynamics of the reaction of C2 with C6H2: an implication for the formation of interstellar C8H.

The reaction C2 + C6H2 → C8H + H was investigated for the first time. Reactant C2 (C6H2) was synthesized from 1% C3F6/He (5% C2H2/He) by pulsed high-voltage discharge. We measured the translational-energy distribution, the angular distribution, and the photoionization spectrum of product C8H in a crossed molecular-beam apparatus using synchrotron vacuum-ultraviolet ionization.

Dynamics of the reaction of C₃(a³Πu) radicals with C₂H₂: a new source for the formation of C₅H.

The reaction C3(a(3)Πu) + C2H2 → C5H + H was investigated at collision energy 10.9 kcal mol(-1) that is less than the enthalpy of ground-state reaction C3(X(1)Σg (+)) + C2H2 → C5H + H. C3(a(3)Πu) radicals were synthesized from 1% C4F6/He by pulsed high-voltage discharge.

Dynamics of carbon-hydrogen and carbon-methyl exchanges in the collision of 3P atomic carbon with propene.

We investigated the dynamics of the reaction of (3)P atomic carbon with propene (C3H6) at reactant collision energy 3.8 kcal mol(-1) in a crossed molecular-beam apparatus using synchrotron vacuum-ultraviolet ionization. Products C4H5, C4H4, C3H3, and CH3 were observed and attributed to exit channels C4H5 + H, C4H4 + 2H, and C3H3 + CH3; their translational-energy distributions and angular distributions were derived from the measurements of product time-of-flight spectra.

Exploring the dynamics of C/H and C/Cl exchanges in the C(3P) + C2H3Cl reaction.

The dynamics of the C((3)P) + C2H3Cl reaction at collision energy 3.8 kcal mol(-1) was investigated in a crossed molecular-beam apparatus using synchrotron vacuum-ultraviolet ionization. Time-of-flight spectra of products C3H2Cl, C3H3, and Cl were recorded at various laboratory scattering angles, from which translational-energy distributions and angular distributions of product channels C3H2Cl + H and C3H3 + Cl were derived.

Dynamics of the C/H and C/F exchanges in the reaction of 3P carbon atoms with vinyl fluoride.

Two product channels C3H2F + H and C3H3 + F were identified in the reaction of C((3)P) atoms with vinyl fluoride (C2H3F) at collision energy 3.7 kcal mol(-1) in a crossed molecular-beam apparatus using selective photoionization. Time-of-flight (TOF) spectra of products C3H2F and C3H3 were measured at 12-16 laboratory angles as well as a TOF spectrum of atomic F, a counter part of C3H3, was recorded at single laboratory angle.

Exploring the dynamics of reaction C(3P) + C2H4 with crossed beam/photoionization experiments and quantum chemical calculations.

We investigated the title reaction at collision energy 3.5 kcal mol(-1) in a crossed molecular beam apparatus using undulator radiation as an ionization source. Time-of-flight (TOF) spectra of product C(3)H(3) were measured in laboratory angles from 20° to 100° using two photoionization energies 9.

Comparison of two-body and three-body decomposition of ethanedial, propanal, propenal, n-butane, 1-butene, and 1,3-butadiene.

We investigated two-body (binary) and three-body (triple) dissociations of ethanedial, propanal, propenal, n-butane, 1-butene, and 1,3-butadiene on the ground potential-energy surfaces using quantum-chemical and Rice-Ramsperger-Kassel-Marcus calculations; most attention is paid on the triple dissociation mechanisms. The triple dissociation includes elimination of a hydrogen molecule from a combination of two separate terminal hydrogen atoms; meanwhile, the rest part simultaneously decomposes to two stable fragments, e.g.

Molecular-beam experiments for photodissociation of propenal at 157 nm and quantum-chemical calculations for migration and elimination of hydrogen atoms in systems C3H4O and C3H3O.

We investigated the dynamics of photodissociation of propenal (acrolein, CH(2)CHCHO) at 157 nm in a molecular beam and of migration and elimination of hydrogen atoms in systems C(3)H(4)O and C(3)H(3)O using quantum-chemical calculations. Compared with the previous results of photodissociation of propenal at 193 nm, the major difference is that the C(3)H(3)O fragment present at the 193-nm photolysis disappears at the 157-nm photolysis whereas the C(3)H(2)O fragment absent at 193 nm appears at 157 nm. Optimized structures and harmonic vibrational frequencies of molecular species with gross formula C(3)H(2-4)O were computed at the level of B3LYP/6-311G(d,p) and total energies of those molecules at optimized structures were computed at the level of CCSD(T)/6-311+G(3df,2p).

Exploring the dynamics of reaction N((2)D)+C2H4 with crossed molecular-beam experiments and quantum-chemical calculations.

We conducted the title reaction using a crossed molecular-beam apparatus, quantum-chemical calculations, and RRKM calculations. Synchrotron radiation from an undulator served to ionize selectively reaction products by advantage of negligibly small dissociative ionization. We observed two products with gross formula C(2)H(3)N and C(2)H(2)N associated with loss of one and two hydrogen atoms, respectively.

Theoretical study of isomerization and decomposition of propenal.

We investigated the dynamics of isomerization and multi-channel dissociation of propenal (CH(2)CHCHO), methyl ketene (CH(3)CHCO), hydroxyl propadiene (CH(2)CH(2)CHOH), and hydroxyl cyclopropene (cyclic-C(3)H(3)-OH) in the ground potential-energy surface using quantum-chemical calculations. Optimized structures and vibrational frequencies of molecular species were computed with method B3LYP∕6-311G(d,p). Total energies of molecules at optimized structures were computed at the CCSD(T)∕6-311+G(3df,2p) level of theory.