Isotopic mixed crystal exciton spectra in the far infrared: Naphthalene

The far infrared vibrational exciton spectra of isotopic mixed crystals of naphthalene-h₈ and d₈ were studied. The two observed translational phonon modes were determined to fall into the amalgamated band limit while the lowest energy B_3u, A_u and B_1u vibrational exciton bands were found to be in the separated band limit. The lowest energy B_3u “butterfly” mode with its large (15 cm^?1) exciton splitting was found to agree well with CPA calculations of mixed crystal spectra. A peak at 185 cm^?1 was also assigned as a peak in the vibrational exciton density-of-states of the B_3u mode.     

The Raman spectra of ferrocene-b10 and -d10: librational modes and comments upon previous polarization data

The librational modes of ferrocene-h₁₀ and -d₁₀ have been observed near 62 cm^?1 (-h₁₀) and 40, 52 and 60 cm^?1 (-d₁₀). The polarization measurements at low temperatures can give no useful information concerning the vibrational assignment until the low temperature crystal structure is completely determined.     

Structure and dynamics of the lowest triplet state in p-benzoquinone: I. An isotope effect study on the optical absorption,emission and ODMR spectra

The results of detailed spectroscopic experiments on the lowest nπ* triplet state of p-benzoquinone-h₄, -dh₃, 2,6-d₂h₂, -d₄ and -CH₃ in mixed and isotopic mixed crystals are presented and analyzed. The origin of the lowest B_1g (nπ*) singlet-triplet transition in p-benzoquinone-h₄ (PBQ-h₄) is shown to be induced by asymmetric isotopic substitution and the oscillator strength of this origin is seen to be accounted for by a corresponding decrease in intensity of a level 16.9 cm^?1 higher in energy in the pure PBQ-h₄ crystal. The combined oscillator strength of these close lying levels is measured and found to be almost independent of deuteration.These results are discussed in reference to the previously proposed double minimum potential model for the lowest nπ* triplet state in PBQ-h₄ and the applicability for this model is critically examined.Optical absorption experiments on heavily doped isotopic mixed crystals of PBQ-h₄ in PBQ-d₄ show hydrogen (deuterium) bounding effects between translational inequivalent molecules to be primarily responsible for the observed cluster states. These hydrogen bounding effects also induce the electronic origin of the B_1g (nπ*) triplet state in case of a translational inequivalent dimer.A detailed vibrational analysis of the phosphorescence spectrum of PBQ-h₄ in a PBQ-d₄ host crystal at 1.8 K is presented and it is shown that the unobserved origin of the B_1g (nπ*) triplet state of PBQ-h₄ is located at 18609 ± 1 cm^?1 and that the inversion splitting in this lowest excited state amounts to 21 ± 1 cm^?1 in this mixed crystal system. An isotope effect is study on the vibronic structure in the emission spectrum further indicates that the excited state structure of PBQ is isotope dependent.The observed large isotope effect on the ZFS parameters of the lowest triplet state of PBQ-h₄ is demonstrated to be an intramolecular phenomenon and explained as an isotope dependent spin-orbit contribution to the ZI-S parameters, induced by localization of the nπ* excitation on oxygen.Finally the dynamics of energy migration in the dilute PBQ-h₄ in PBQ-d₄ isotopic mixed crystal is probed by concentration and temperature dependent phosphorescence intensity measurements and it is suggested that trap-exciton band communication effects are of importance in this system.     

A time-resolved lif study of the kinetics of OH(ν = 0) and OH(ν = 1) with HCl and HBr

The kinetics of OH(ν = 0) and OH(ν = 1) have been followed using pulsed photolysis of H₂O or HNO₃ to generate hydroxyl radicals, and time-resolved, laser-induced fluorescence to observe the rates of their subsequent removal in the presence of HCl or HBr. The experiments yield the following rate constants (cm³ molecule^?1 s^?1) at 298 ± 4 K: OH(ν = 0) + HCl: k_o = (6.8 ± 0.25) × 10^?13; OH(ν = 0) + HBr: k_o = (11.2 ± 0.45) × 10^?12; OH(ν = 1) + HCl: k₁ = (9.7 ± 1.0) × 10^?13; OH(gn = 1) + HBr; k₁ = (8.1 ± 1.05) × 10^?12 For OH(ν = 1), the measurements do not distinguish between loss by reaction and relaxation, and the fact that k₁ > k_o for HCl is tentatively attributed to relaxation, probably by near-resonant vibrational—vibrational energy transfer. Clearly, neither of these exothermic, low-activation-energy reactions is enhanced to any great extent, if at all, by vibrational excitation of the OH radical.ft]*|Present address: Battelle/Pacific Northwest Laboratories, P.O. Box 999, Richland, Washington 99352, USA.     

Fluorescence spectra of the mixed crystal system anthracene-perdeuteroanthracene. Mixed exciton band

The fluorescence spectra of the mixed crystal system anthracene (A-h₁₀)-perdeuteroanthracene (Ad₁₀) have been studied over the full concentration range at temperatures between 1.6 and 77°K. There exists a collective (mixed) A-h₁₀-A-d₁₀ S₁ exciton band at all concentrations, the lower edge of which represents the emitting level for the intrinsic fluorescence at low temperatures. This edge shifts from 25097 cm^?1 in the neat A-h₁₀ crystal to 25156 cm^?1 in the neat A-d₁₀ crystal. The edge position is a non-linear function of the mixed crystal concentration. From that one gets the “critical” distances U_cr⁺ = 92 cm^?1 and U_cr^? = 131 cm^?1 between the molecular S₁ levels of a guest and the host anthracene (non-deuterated or deuterated), using a formula given by Lifshitz. For the critical distance U_cr⁺ one finds just a bound guest state above the host band, and for U_cr^?1 a bound guest state below the host band.The transition from the S₁ band edge to the S₀ ground state is always forbidden, in the same way as in the neat A-h₁₀ crystal. Only transitions to levels of intramolecular and lattice vibrations of the ground state have been observed. At all concentrations the fluorescence transitions from the lower S₁ band edge of the mixed crystal take place to the vibronic levels of both A-h₁₀ and A-d₁₀. The difference in the frequencies of equivalent intramolecular vibrations of A-h₁₀ and A-d₁₀ results in the appearance of vibronic doublets in the intrinsic fluorescence. The relative intensities of the two doublet components depend strongly on both concentration and temperature. This is due to the influence of quasi-resonance and exciton-superexchange upon the guest states inside the mixed exciton band.For all concentrations one observes two transitions originating from levels inside the S₁ exciton band.     

CN stretching and NO2 deformation vibrations and normal coordinate analysis of m-dinitrobenzene and m-dinitrobenzene-d4

Two bands appear for each CN stretching and nitro deformation vibration in the infrared and Raman spectra of m-dinitrobenzene and m-dinitrobenzene-d₄. The 907 cm^?1 bending mode in the vibrational spectra of m-dinitrobenzene undergo 30 cm^?1 upward shift upon d₄ substitution. A normal coordinate analysis pointed out that the 937 cm^?1 bending and 727 cm^?1 CN stretching vibrations as well as 18b CD in-plane deformation are mixed to a great extent. The other nitro bending mode undergo also an inverse isotopic effect (2 cm^?1 upward shift) due to coupling with the 18a CD in-plane deformation vibration.     

The intrinsic fluorescence of the mixed crystal system anthracene-perdeuteroanthracene, amalgamated exciton band

The fluorescence spectra of the mixed crystal system anthracene (A-h₁₀) - perdeuteroanthracene (A-d₁₀) have been studied over the full concentration range at temperatures between 1.6 and 77 K. There exists an amalgamated A-h₁₀ - A-d₁₀ S₁ exciton band at all concentrations. The intrinsic fluorescence starts from the lower edge this S₁ band at low temperatures. The edge shifts with a non-linear dependence with increasing concentration from 25097 cm⁻¹ in the neat A-h₁₀ crystal to 25156 cm⁻¹ in the neat A-d₁₀ crystal. The transition from the S₁ band edge to the S₀ ground state is always forbidden. Only transitions to levels intramolecular and lattice vibrations of the ground state have been observed. The fluorescence transitions take place to vibrational levels of both A-h₁₀ and A-d₁₀. This leads to a doublet structure of the vibrational bands. Due to the influence of quasi-resonance and exciton-superexchange the transitions to A-h₁₀ vibrational states at low temperatures are more probable than it would correspond to the A-h₁₀ concentration. Using the concentration shift of the lower S₁ band edge an approximative determination of the energy exchange integral square sum to Σ M² = 9600 cm⁻² ± 50% is possible.     

Crystal field effects on the ground and lowest excited triplet states of benzene isotopes in a borazine host crystal

The phosphorescence spectra of the C₆H₆C₆H₅D₁p-C₆H₄D₂symp-C₆H₃D₃, C₆D₆ and ¹³CC₅D in a borazine host crystal are analyzed at high resolution. The spectral lines are sharp (～2 cm^?1 wide) indicating that the impurity molecules occupy a unique site in the borazine lattice which is probably substitutional. The phonon sidebands are weak,giving clean, well-resolved spectra much like those of isotopic mixed crystals. In contrast, however, the crystal field effects on the ground state vibrational levels are much smaller than those found for isotopic mixed crystals. The gas-to-crystal shifts are very small, the vibrational degeneracies are not removed and orientational splittings are only observable for a few select vibrational levels. For most vibrational levels and for the derivation of selection rules one can asume the effective crystal site symmetry to be D_3d. The data provide the first conclusive evidence that the splitting observed in the benzene phosphorescence spectrum results from a distortion of the molecule when excited to the zeroth vibrational level of the T₁ state. Furthermore, the data suggest that the distortion is intrinsic in nature (i.e.,is not caused by the crystal field).     

Photon-echo relaxation measurements with two dye-lasers application to pentacene-h14 and -d14 in p-terphenyl-h crystals at 1.5 K

Electronically controlled photon-echo relaxation measurements, using two nitrogen pumped dye-lasers, are reported for mixed crystals of pentacene-h₁₄ and -d₁₄ in p-terphenyl-h₁₄ at 1.5 K. In dilute mixed crystals (ca. 10^?8 M) the photon-echo lifetime is found to be exclusively determined by the fluorescence lifetime. Homogeneous linewidths of 7.1 and 5.9 MHz at 1.5 K are then calculated for the electronic origin of the ¹B_2u ← ¹A_1g transition of pentacene-h₁₄ and -d₁₄ respectively. The decrease in photon-echo lifetime at higher guest concentrations (ca. 10^?7 M) is ascribed to energy transfer between excited and neutral guest molecules.     

Equilibrium structure and vibrational frequencies of the O4 molecule

SCF closed shell calculations were performed to determine the equilibrium structure and vibrational frequencies of the O₄ molecule by means of Payne's method and with the help of the molecule's symmetry coordinates. The equilibrium geometry corresponds to symmetry group D_2d with R = 1.505 Å and h = 0.094 Å. The vibrational frequencies are: ν₅(E) = 885.5 cm^?1, ν₃(B₁) = 1051.9 cm^?1, ν₁(A₁) = 1018.3 cm^?1, ν₄(B₂) = 880.3 cm^?1. The second vibrational coordinate (A₁) corresponds to a double-well potential. The first vibrational levels were calculated by a variational method.     

The relaxation of HCl(ν = 1) and DCl(ν = 1) by O atoms between 196 and 400 K

The rates of relaxation of HCl(ν = 1) and DCl(ν = 1) by atomic oxygen have been determined between 196 and 400 K using the laser induced vibrational fluorescence method. The values of the rate constants, κ_1,H and κ_1,D, can be matched quite well by Arrhenius expressions: κ_1,H = 6.2 × 10^?12 exp (?1.0₅ kcal mole^?1/RT) cm³ molecule^?1 s^?1 and κ_1,D = 2.9 × 10^?12 exp (?0.5 kcal mole^?1/RT) cm³ molecule^?1 s^?1. The most likely explanation of the absolute and relative magnitudes of these rate constants appears to be that relaxation occurs as a result of non-adiabatic vibronic transitions during collisions.     

Raman analysis of SF6 molecular beams excited by a cw CO2 laser

In a molecular beam the effects of vibrational pumping of SF₆ (ν₃ = 948 cm^?1) are studied, using a line-tunable cw CO₂ laser. Intracavity spontaneous Raman scattering is used for analysis. For excitation in the collision regime (x_E/D ≤ 1), a thermal redistribution of the ν₃ excitation over all vibrational modes is found, together with an average absorption up to six photons per molecule. The infrared absorption profile shows a red-shift of 6 cm^?1. For excitation in the relatively rare collision regime (x_E/D ? 4), a structured non-thermal ν₁ Raman spectrum is observed, especially in the case of seeded molecular beams (10% in He). The observed hot-band peaks can be explained in terms of single-photon absorptions and collision-induced near-resonant V-V energy transfer, leading to single, double and triple excitations of the ν₃ mode. The value of T_rot in the beam is found to influence sensitively the non-resonant energy-transfer rate [e.g. hν₃(948 cm^?1)+ΔE_rot → h(ν₄ + ν₆)(962 cm^?1) relative to the near-resonant transfer rate (hν₃ + hν₃ → 2hν₃ + 3.5 cm^?1)].     

Metal ion distribution and solubility of Mn1−xCux(HCOO)2 · 2 H2O Mixed Crystals [1–5]

The metal ion distribution on the two metal sites of monoclinic Mn_1?xCu_x(HCOO)₂ · 2(H,D)₂O mixed crystals are studied by infrared and Raman spectroscopic methods. The spectral regions 3 200–3 400 cm^?1 (v_OH), 2 875–2 990 cm^?1 (v_CH), 2 330–2 500 cm^?1 (v_OD of matrix isolated HDO molecules), 1 350–1 400 cm^?1 (symmetric CO₂ stretching modes), 570–950 cm^?1 (H₂O librations), and 490 cm^?1 (M? O lattice modes) are mostly sensitive to the metal ions present. The frequency shifts of these bands with increasing content of copper show that Cu²⁺ prefers the M(1) site, coordinated by HCOO^? only. The strengths of the hydrogen bonds increase on going from manganese to copper formate, due to the increased synergetic effect of Cu²⁺. Solubility and X-ray data of the mixed crystals are included. Irrespective of the same crystal structure, two series of mixed crystals are formed: eutonic area at 0.65 ≥ x ≥ 0.5.     

Laser raman spectra of the stable low-temperature phase of ferrocene

Laser Raman spectra of ferrocene crystal are recorded for the stable (orthorhombic) and metastable (triclinic) low-temperature phases, and the stable and undercooled (monoclinic) high-temperature phases.The skeletal vibrational modes [v₄(A_1g) and v₁₆(E_1g)], the CH bending (⊥e) mode [v₂₅(E_2g)], and the lattice modes below 100 cm^?1 show characteristic changes among these phases.     

Infrared and raman spectra,vibrational assignment and barriers to internal rotation for methyldisilylamine

The Raman spectra of gaseous and liquid (SiH₃)₂NCH₃ and (SiH₃)₂NCD₃ have been recorded to within 10 cm^?1 of the exciting line. The IR spectra of (SiH₃)₂NCH₃ and (SiH₃)₂NCD₃ have been recorded from 80 cm^?1 to 3800 cm^?1 in the gaseous state, and from 80 cm^?1 to 450 cm^?1 in the solid state. A vibrational assignment has been made, and from the low-frequency vibrational data, an upper limit of 3.3 kcal mol^?1 was calculated for the barrier to internal rotation of the silyi groups, whereas a barrier of ~450 cal was calculated for internal rotation of the methyl group. It is concluded that there exists a significantly strong d_π—p_π interaction in methyldisilylamine.     

Assignment and analysis of the absorption and emission spectra of the lowest nπ* triplet state in 9,10-anthraquinone

Polarized Zeeman absorption experiments on 9,10-anthraquinone crystals show the lowest triplet state in this molecule to be a g nπ^* state. The gap between this state and the higher u nπ^* state is found to be 410 cm^?1. The phosphorescence spectrum of an isotopically mixed crystal of AQ-h₈ in AQ-d₈ is analyzed in detail and confirms the orbitally forbidden nature of the emitting state. The results are compared with those previously obtained for p-benzoquinone.     

Low-frequency vibrations of molecular solids: XV. Globular molecule 1,2-dichloroethane

The far infrared and Raman spectra of polycrystalline 1,2-dichloroethane and 1,2-dichloroethane-d₄ for the low temperature modification have been measured from 450 to 33 cm⁻¹ at various temperatures from −100 to −182°C. Raman spectra of the high temperature crystalline modification for both samples were also investigated. The Raman data are in conflict with those previously reported. Assignments are made for the lattice vibrations in terms of the crystallographic unit cell C_2h⁵ (P_21/c) with two molecules per unit cell. The spectra of the high temperature modification are consistent with those expected for orientationally disordered crystals.     

Time resolved fluorescence of anthracene in mixed crystals at 2K

An optical Kerr shuttered spectrograph has been used to time resolve the spontaneous fluorescence of aromatic mixed crystal systems at low temperature with moderate resolution. Transient effects on the fluorescence of anthracene in naphthalene excited with 614 cm^?1 vibrational excess energy in ¹B_2u have been observed that may signal measurable vibrational relaxation pathways. A model consistent with these observations is presented: it implicates a strong interaction between the intramolecular Franck—Condon and non-Franck—Condon modes in the relaxation process for specific excitation in the region of large excess lattice energy. Examination of the fluorescence for several aromatic systems integrated over the interval 0 to 30 ps following excitation high in the S₁ vibrational manifold failed to reveal evidence of non-Boltzmann vibrational distributions, although other largely unexplained effects have been observed.     

Vibrational relaxation in neat crystals of naphthalene by picosecond cars

Picosecond delayed CARS experiments on totally symmetric modes in naphthalene at 1.5 K are reported. The Raman lineshape of the vibrational excitons is lorentzian and vibrational relaxation can be surprisingly slow. The Raman lineshape of the A_g exciton level of the 766 cm^?1 vibrational mode reveals that the low-temperature lorentzian lineshape occurs by motional narrowing At higher temperature the exciton is trapped by interaction with lattice phonons.     

Structural stability and vibrational analysis of beryllium sulfide BeS from the bulk to the (n,0) nanotubes. An ab initio description

Beryllium sulfide (BeS) in different forms from molecule, bulk, monolayer (h-BeS), to the single-walled nanotube obtained by wrapping the h-BeS monolayer along the (n,0) hexagonal lattice vector for n varying from n = 6 to 64, has been examined. Density functional theory (DFT) with an all electron basis set and the hybrid DFT/B3LYP level have been applied to compute energetic and geometrical, electronic and vibrational, elastic and piezoelectric properties, where the trend towards the hexagonal monolayer (h-BeS) in the limit of large tube radius is obtained. The vibrational properties including Raman spectra and polarizabilities are evaluated via the Coupled Perturbed Hartree–Fock and Kohn–Sham (CPHF/KS) computational schemes. For the first time, the IR vibrational modes at higher tube diameter and their convergence to the h-BeS monolayer limit are reported where the vibrational and electronic contributions to both perpendicular and parallel components of polarizability tensor are additionally discussed. For the (n,0) BeS nanotube family, three ranges of IR active phonon modes are determined. The first one located in the 0–300 cm⁻¹frequency domain, goes regularly to zero when the tube diameter increases. Both the second (300–400 cm⁻¹) and the third (700–800 cm⁻¹) ones tend smoothly with different slope, towards the two optical vibrational modes of the h-BeS layer. These theoretical models can be extended to investigate further issues, such as the effect caused by the addition of a dopant, the influence of the substitutional fraction of nanotube atoms and the interaction of molecules outside and/or inside of the nanotube.