Rovibrational Spectra of LiH₂⁺, LiHD⁺ and LiD₂⁺ Determined from FCI Property Surfaces

Full configuration interaction (FCI) has been used in conjunction with the lithium [6s5p3d1f] (Iron, M. A.; et al. Mol. Phys. 2004, 101, 1345) and hydrogen aug-cc-pVTZ basis sets to construct an 83-point potential energy surface of the 1A1 ground state of 7LiH2+. Vibrational and rovibrational wave functions of the6,7LiH2+, 6,7LiHD+, and 6,7LiD2+ ground states were calculated variationally using an Eckart−Watson Hamiltonian. For 7LiD2+, rovibrational transition frequencies for K = 0, 1, 2 and J ≤ 10 are within ca. 0.1% of recent experimental values (Thompson, C. D.; et al. J. Chem. Phys. 2006, 125, 044310). A 47-point FCI dipole moment surface was embedded in the rovibrational Hamiltonian to calculate vibrational and rovibrational radiative properties. At 296 K, with v ≤ 4 and J ≤ 4, the 202 ← 303 rotational transition in the |001〉 band was found to have the greatest spectral intensity with respect to the ground electronic states of 6,7LiH2+, 6,7LiHD+, and 6,7LiD2+. In each case, the most intense rovibrational transitions have been assigned unequivocally using the J, Ka, Kc assignment scheme

Rovibrational Spectra of LiH₂⁺, LiHD⁺ and LiD₂⁺ Determined from FCI Property Surfaces

Full configuration interaction (FCI) has been used in conjunction with the lithium [6s5p3d1f] (Iron, M. A.; et al. Mol. Phys. 2004, 101, 1345) and hydrogen aug-cc-pVTZ basis sets to construct an 83-point potential energy surface of the 1A1 ground state of 7LiH2+. Vibrational and rovibrational wave functions of the6,7LiH2+, 6,7LiHD+, and 6,7LiD2+ ground states were calculated variationally using an Eckart−Watson Hamiltonian. For 7LiD2+, rovibrational transition frequencies for K = 0, 1, 2 and J ≤ 10 are within ca. 0.1% of recent experimental values (Thompson, C. D.; et al. J. Chem. Phys. 2006, 125, 044310). A 47-point FCI dipole moment surface was embedded in the rovibrational Hamiltonian to calculate vibrational and rovibrational radiative properties. At 296 K, with v ≤ 4 and J ≤ 4, the 202 ← 303 rotational transition in the |001〉 band was found to have the greatest spectral intensity with respect to the ground electronic states of 6,7LiH2+, 6,7LiHD+, and 6,7LiD2+. In each case, the most intense rovibrational transitions have been assigned unequivocally using the J, Ka, Kc assignment scheme

Rovibrational Spectra of LiH₂⁺, LiHD⁺ and LiD₂⁺ Determined from FCI Property Surfaces

Full configuration interaction (FCI) has been used in conjunction with the lithium [6s5p3d1f] (Iron, M. A.; et al. Mol. Phys. 2004, 101, 1345) and hydrogen aug-cc-pVTZ basis sets to construct an 83-point potential energy surface of the 1A1 ground state of 7LiH2+. Vibrational and rovibrational wave functions of the6,7LiH2+, 6,7LiHD+, and 6,7LiD2+ ground states were calculated variationally using an Eckart−Watson Hamiltonian. For 7LiD2+, rovibrational transition frequencies for K = 0, 1, 2 and J ≤ 10 are within ca. 0.1% of recent experimental values (Thompson, C. D.; et al. J. Chem. Phys. 2006, 125, 044310). A 47-point FCI dipole moment surface was embedded in the rovibrational Hamiltonian to calculate vibrational and rovibrational radiative properties. At 296 K, with v ≤ 4 and J ≤ 4, the 202 ← 303 rotational transition in the |001〉 band was found to have the greatest spectral intensity with respect to the ground electronic states of 6,7LiH2+, 6,7LiHD+, and 6,7LiD2+. In each case, the most intense rovibrational transitions have been assigned unequivocally using the J, Ka, Kc assignment scheme

Rovibrational Spectra of LiH₂⁺, LiHD⁺ and LiD₂⁺ Determined from FCI Property Surfaces

Full configuration interaction (FCI) has been used in conjunction with the lithium [6s5p3d1f] (Iron, M. A.; et al. Mol. Phys. 2004, 101, 1345) and hydrogen aug-cc-pVTZ basis sets to construct an 83-point potential energy surface of the 1A1 ground state of 7LiH2+. Vibrational and rovibrational wave functions of the6,7LiH2+, 6,7LiHD+, and 6,7LiD2+ ground states were calculated variationally using an Eckart−Watson Hamiltonian. For 7LiD2+, rovibrational transition frequencies for K = 0, 1, 2 and J ≤ 10 are within ca. 0.1% of recent experimental values (Thompson, C. D.; et al. J. Chem. Phys. 2006, 125, 044310). A 47-point FCI dipole moment surface was embedded in the rovibrational Hamiltonian to calculate vibrational and rovibrational radiative properties. At 296 K, with v ≤ 4 and J ≤ 4, the 202 ← 303 rotational transition in the |001〉 band was found to have the greatest spectral intensity with respect to the ground electronic states of 6,7LiH2+, 6,7LiHD+, and 6,7LiD2+. In each case, the most intense rovibrational transitions have been assigned unequivocally using the J, Ka, Kc assignment scheme

Boron Nitride Nucleation Mechanism during Chemical Vapor Deposition

We present nonequilibrium molecular dynamics simulations demonstrating how boron nitride (BN) nanomaterials nucleate during boron oxide chemical vapor deposition (CVD). Chemical reactions between gas-phase B2O2 and NH3 precursors lead to the nucleation and growth of BN nanostructures in the presence of a boron nanoparticle. The formation of BN rings is mediated by the boron nanoparticle and is promoted by the formation of H2O. Gas-phase H2 is also produced during this process; however, we demonstrate that H2 and H2O formation serves two distinctly different roles during BN nucleation. H2 formation promotes the clustering of BxOx species to form catalytic B nanoparticles; H2O formation promotes BN bond formation and ultimately BN ring condensation, both in the gas phase and at the nanoparticle surface. Thermal annealing of amorphous BN networks formed via this reaction undergo defect healing over significant simulation times (∼20 ns) to afford tube-like BN nanostructures

Polyyne Chain Growth and Ring Collapse Drives Ni-Catalyzed SWNT Growth: A QM/MD Investigation

A mechanism describing Ni38-catalyzed single-walled carbon nanotube (SWNT) growth has been elucidated using quantum mechanical molecular dynamics (QM/MD) methods. This mechanism is dominated by the existence of extended polyyne structures bound to the base of the initial SWNT cap-fragment. Polygonal ring formation, and hence SWNT growth itself, was driven by the continual, simultaneous extension of these polyyne chains and subsequent “ring collapse” (i.e., self-isomerization/interaction of these polyyne chains). The rate of the former exceeded that of the latter, and so this mechanism was self-perpetuating. Consequently, the observed kinetics of Ni38-catalyzed SWNT growth were increased substantially compared to those observed using other transition metal catalysts of comparable size

Polyyne Chain Growth and Ring Collapse Drives Ni-Catalyzed SWNT Growth: A QM/MD Investigation

A mechanism describing Ni38-catalyzed single-walled carbon nanotube (SWNT) growth has been elucidated using quantum mechanical molecular dynamics (QM/MD) methods. This mechanism is dominated by the existence of extended polyyne structures bound to the base of the initial SWNT cap-fragment. Polygonal ring formation, and hence SWNT growth itself, was driven by the continual, simultaneous extension of these polyyne chains and subsequent “ring collapse” (i.e., self-isomerization/interaction of these polyyne chains). The rate of the former exceeded that of the latter, and so this mechanism was self-perpetuating. Consequently, the observed kinetics of Ni38-catalyzed SWNT growth were increased substantially compared to those observed using other transition metal catalysts of comparable size

Rovibrational Spectra of LiH₂⁺, LiHD⁺ and LiD₂⁺ Determined from FCI Property Surfaces

Full configuration interaction (FCI) has been used in conjunction with the lithium [6s5p3d1f] (Iron, M. A.; et al. Mol. Phys. 2004, 101, 1345) and hydrogen aug-cc-pVTZ basis sets to construct an 83-point potential energy surface of the 1A1 ground state of 7LiH2+. Vibrational and rovibrational wave functions of the6,7LiH2+, 6,7LiHD+, and 6,7LiD2+ ground states were calculated variationally using an Eckart−Watson Hamiltonian. For 7LiD2+, rovibrational transition frequencies for K = 0, 1, 2 and J ≤ 10 are within ca. 0.1% of recent experimental values (Thompson, C. D.; et al. J. Chem. Phys. 2006, 125, 044310). A 47-point FCI dipole moment surface was embedded in the rovibrational Hamiltonian to calculate vibrational and rovibrational radiative properties. At 296 K, with v ≤ 4 and J ≤ 4, the 202 ← 303 rotational transition in the |001〉 band was found to have the greatest spectral intensity with respect to the ground electronic states of 6,7LiH2+, 6,7LiHD+, and 6,7LiD2+. In each case, the most intense rovibrational transitions have been assigned unequivocally using the J, Ka, Kc assignment scheme

Rovibrational Spectra of LiH₂⁺, LiHD⁺ and LiD₂⁺ Determined from FCI Property Surfaces

Full configuration interaction (FCI) has been used in conjunction with the lithium [6s5p3d1f] (Iron, M. A.; et al. Mol. Phys. 2004, 101, 1345) and hydrogen aug-cc-pVTZ basis sets to construct an 83-point potential energy surface of the 1A1 ground state of 7LiH2+. Vibrational and rovibrational wave functions of the6,7LiH2+, 6,7LiHD+, and 6,7LiD2+ ground states were calculated variationally using an Eckart−Watson Hamiltonian. For 7LiD2+, rovibrational transition frequencies for K = 0, 1, 2 and J ≤ 10 are within ca. 0.1% of recent experimental values (Thompson, C. D.; et al. J. Chem. Phys. 2006, 125, 044310). A 47-point FCI dipole moment surface was embedded in the rovibrational Hamiltonian to calculate vibrational and rovibrational radiative properties. At 296 K, with v ≤ 4 and J ≤ 4, the 202 ← 303 rotational transition in the |001〉 band was found to have the greatest spectral intensity with respect to the ground electronic states of 6,7LiH2+, 6,7LiHD+, and 6,7LiD2+. In each case, the most intense rovibrational transitions have been assigned unequivocally using the J, Ka, Kc assignment scheme