Single-molecule conductance determinations on HS(CH2)4O(CH2)4SH and HS(CH2)2O(CH2)2O(CH2)2SH, and comparison with alkanedithiols of the same length

The acetyl-protected, thiol-terminated ethers AcS(CH(2))(4)O(CH(2))(4)SAc and AcS(CH(2))(2)O(CH(2))(2)O(CH(2))(2)SAc have been synthesised, and a range of related scanning tunnelling microscopy (STM)-based methods have been employed to fabricate and electrically characterise gold | single molecule | gold junctions involving these molecules. The single-molecule conductance values obtained are consistently found to be substantially higher (by a factor of 2-3) than the conductances of analogous alkanedithiols of similar length (HS(CH(2))(9)SH and HS(CH(2))(8)SH, respectively). A rationalisation of these findings is suggested, namely that the lone pair electrons on the oxygen atoms are substantially closer in energy to the Fermi energy of the gold leads than are the occupied and unoccupied states of methylene chains, so that the ether oxygens behave in a manner analogous to 'wells' in a double-tunnelling-barrier system. In agreement with this suggestion, the current-voltage behaviour of the monoether can be fitted using the Simmons approach, and the barrier height is found to be significantly lower than for alkanedithiols of approximately the same length.     

Barriers to internal rotation and tunnelling splittings of the torsional states in the HO(CH2)OH,DO(CH2)OH and DO(CH2)OD molecules

Torsional states caused by vibrations of hydroxyl groups in the methanediol molecule and its two deuterated analogues – DO(CH₂)OH and DO(CH₂)OD were analysed at MP2/cc-pVTZ and CCSD(T)/cc-pVQZ levels of theory. In the first case, 2D PES and 2D surfaces of kinematic coefficients were calculated with geometry optimisation for all other geometric parameters, and in the second case, only the energy of optimised configurations at the MP2/cc-pVTZ level of theory was determined. Then 2D PES was recounted to the complete basis set (CBS) limit by extrapolating the results of calculations at the MP2/cc-pVTZ and MP2/cc-pVQZ levels of theory The calculated values were then averaged over four equivalent points on the coordinate plane. Hamiltonian matrices were constructed using DVR and Fourier methods. After their subsequent diagonalization, the energies of the stationary torsional states were computed. Their classification by C_2V(M) and C_S(M) molecular symmetry groups has been performed. The splitting values due to the tunnelling of the thirty most deeply located torsional states in the three studied molecules were also determined. The torsional states, internal rotation barriers, and tunnelling frequencies in the molecules of methanediol and hydrogen trioxide were compared.     

Mechanistic study of the reaction of methyl peroxy radical (CH3O2) with formaldehyde (CH2O)

ABSTRACT

A direct dynamic study on the reactions of CH₃O₂?+?CH₂O was carried out over the temperature range of 300–1500?K. All stationary points were calculated with the M06-2X/6-311++G(d,p) level of theory and identified for local minimum. The energetic parameters were refined at QCISD (T)/cc-pVTZ and CCSD (T)/cc-pVTZ levels of theory. Three channels were explored and a reaction of hydrogen abstraction from CH₂O by CH₃O₂ was identified as dominant channel which involves the formation of a prereactive complex in the entrance channel. The rate coefficient of the dominant channel was calculated with TST and TST/Eck and the Eckart tunnelling effect is only important over the lower temperature region. The calculated rate coefficient of the dominant channel has positive temperature dependence and agrees reasonably with the available literature data.     

Calculation of the normal modes of CH3OP(s)Cl2 and (CH3O)2P(S)Cl

Frequency and form are deduced for the normal modes. The calculated and observed deformation frequencies of the CH₃O group agree only if the force field of that group has C_S symmetry. The C-O, P-O, P=S, and P-Cl modes are examined for characteristic behavior. The integral intensities of the corresponding bands are reported for trichlorothiophosphate, methyldichlorothiophosphate, dimethylchlorothiophosphate, and trimethylthiophospate.The behavior of the integral intensity of the P=S band is discussed.     

Spectral reflectance of the one-dimensional organic metals (perylene)2(PF6)1.1 × 0.8CH2Cl2 and (perylene)2(AsF6)1.1 × 0.7CH2Cl2

We report on the optical reflectance of (perylene)₂(PF₆)_1.1 × 0.8CH₂Cl₂ and (perylene)₂(AsF₆)_1.1 × 0.7CH₂Cl₂ single crystals in the energy range from 0.25 to 4 eV. For light polarized perpendicular to the molecular stacks the crystals exhibit the optical behaviour of an insulating molecular crystals, whereas for light polarized parallel to the stacks a pronounced plasma edge at $\text{h}\text{?}\text{ω = 0.9}\text{eV}$ is observed. The experimental data were analyzed by a Lorentz-Drude model in order to determine the electrical conductivity, the carrier concentration, the effective mass, the collision time, the band width, and the Fermi vector of the crystals.     

Optical properties of the proton conductor (NH2(CH3)2)2CoCl4

Based on the data from optical-spectral studies of (NH₂(CH₃)₂)₂CoCl₄ crystals, the existence of high-temperature phase transitions at 419, 380, 352, and 313 K is confirmed. It was shown that with the exception of the first transition, they are related to a considerable extent to rearrangement of the network of hydrogen bonds and are not accompanied by, considerable deformation of the lattice. In this connection the character of the electron-phonon interaction remains unchanged in the entire temperature range of the measurements. The (NH₂(CH₃)₂)₂CoCl₄ structure at room temperature is close to that of the ordered low-temperature phases of such isomorphous crystals as β-K₂SO₄. I. Franko State University, L’vov, Ukraine, 8, Kirill and Mefodii St., UA-290005, L’vov. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 3, pp. 412–418, May–June, 1998.     

(NH_2CH_2COOH)_2CdCl_2晶体的拉曼光谱的研究

（ＮＨ２ＣＨ２ＣＯＯＨ）２ＣｄＣｌ２晶体的拉曼光谱的研究刘建军吴粤郑吉民扈士芬蓝国祥（南开大学天津３０００７１）ＲａｍａｎＳｐｅｃｔｒａｏｆ（ＮＨ２ＣＨ２ＣＯＯＨ）２ＣｄＣｌ２ＣｒｙｓｔａｌｓＬｉｕＪｉａｎｊｕｎ，ＷｕＹｕｅ，ＺｈｅｎｇＪｉｍｉｎ，Ｈ...     

Structures and thermochemistry of methyl ethyl sulfide and its hydroperoxides: HOOCH2SCH2CH3, CH3SCH(OOH)CH3, CH3SCH2CH2OOH,and radicals

Hydroperoxides and the corresponding peroxy radicals are important intermediates during the partial oxidation of methyl ethyl sulfide (CH₃SCH₂CH₃) in both atmospheric chemistry and in combustion. Structural parameters, internal rotor potentials, bond dissociation energies, and thermochemical properties (ΔH_f^o, S^o and C_p(T)) of 3 corresponding hydroperoxides CH₂(OOH)SCH₂CH₃, CH₃SCH(OOH)CH₃, CH₃SCH₂CH₂OOH of methyl ethyl sulfides, and the radicals formed via loss of a hydrogen atom are important to understanding the oxidation reactions of MES. The lowest energy molecular structures were identified using the density functional B3LYP/6‐311G(2d,d,p) level of theory. Standard enthalpies of formation (ΔH_f^o₂₉₈) for the radicals and their parent molecules were calculated using the density functional B3LYP/6‐31G(d,p), B3LYP/6‐31 + G(2d,p), and the composite CBS‐QB3 ab initio methods. Isodesmic reactions were used to determine ?H_f^o values. Internal rotation potential energy diagrams and rotation barriers were investigated using the B3LYP/6‐31G(d,p) level theory. Contributions for S^o₂₉₈ and C_p(T) were calculated using the rigid rotor harmonic oscillator approximation based on the structures and vibrational frequencies obtained by the density functional calculations, with contributions from torsion frequencies replaced by internal rotor contributions. The recommended values for enthalpies of formation of the most stable conformers of CH₃SCH₂CH_2, CH₂(OOH)SCH₂CH₃, CH₃SCH(OOH)CH₃, and CH₃SCH₂CH₂OOH are ?14.0, ?33.0, ?37.2, and ?32.7 kcal/mol, respectively. Group additivity values were developed for estimating properties of structurally similar and larger sulfur‐containing peroxides. Groups for use in group additivity estimation of sulfur peroxide thermochemical properties were developed.     

Near UV Spectra of the Aniliniums: φCH+ 2CH2X, φNH+ (CH2Xa)CH2Xb and φNH+ (C2H4)2X. Long Range Interactions Involving φ and X

We have shown in preceding papers^(1–3), in a study of some specific anilinium ions such as φNH⁺ _3-n (CH₃)_n, φ₂NH⁺ ₂ and φ₃NH⁺, that varying the ammonium groups, or the medium, can lead to great changes in the intensity of the secondary transition of the chromophore^(1–4) because of a δ, π coupling involving the substituent ^(1–10) and φ. In the present work we should like to extend our experiments to more complex ions - since apart our own works the UV spectroscopy of the aniliniums is almost unknown - to study the sensitivity of the chromophore to long range interactions with X through space or through the bonds of the substituents^(11–16).     

The angleICI Bending Satellites in the Millimeter-Wave Rotational Spectra of CH(2)I(2) and CD(2)I(2)

Rotational transitions in the first four excited states of the low-frequency angleICI bending mode, nu(4), have been assigned in the mm-wave rotational spectra of CH(2)I(2) and of CD(2)I(2). Measurements of transition frequencies, made over the frequency region 167-326 GHz and for J" up to 190, allowed determination of sextic level spectroscopic constants for all states. The changes in spectroscopic constants with vibrational excitation show very small anharmonicity, in spite of the very low frequency of this mode (121 cm(-1)). Vibrational excitation affects the moments of inertia in such a way that the planar moment P(b), about the plane perpendicular to both angleICI and angleHCH, is practically invariant. Vibrational change in P(c), the moment along the principal axis in the HCH plane and perpendicular to the angleHCH bisector, has been successfully reproduced with an ab initio harmonic force field so that there is no discernible vibrational change in angleHCH on excitation of angleICI. Finally, the change in P(a) leads to estimated vibrational change of +0.12 degrees in the value of angleICI itself. Copyright 2000 Academic Press.     

Improvement of spectral editing in solids: A sequence for obtaining (13)CH + (13)CH(2)-only (13)C spectra

An improved spectral editing method for solids is described which allows one to obtain a set of subspectra in roughly two-thirds the amount of time as our original CPPI editing method for the same signal to noise. This improvement is afforded by a new pulse sequence that is used to acquire a (13)CH + (13)CH(2) spectrum which has very little (13)CH(3) or nonprotonated carbon contamination. By using this new sequence the (13)CH-only subspectrum is obtained much more efficiently. Criteria for optimizing the signal to noise in the edited subspectra are discussed. Copyright 2000 Academic Press.     

Vibrational Spectra of Dimethyldithiophosphinate Anion: (CH3)2PS2

Abstract

The infrared and Raman spectra of dimethyldithiophosphinate anion (CH₃)₂PS₂ were measured and the vibrational modes for the anion complex were assigned. A Normal Coordinate Analysis in the Modified General Valence Force Field (MGVFF) approximation was carried out assuming C_2v symmetry. Ab Initio Calculations at RHF and MP2 level were also carried out for the anion geometry as well as for its frequencies, intensities and force constants.     

2J,(3)J-HMBC: A new long-range heteronuclear shift correlation technique capable of differentiating (2)J(CH) from (3)J(CH) correlations to protonated carbons

The development of a series of new, accordion-optimized long-range heteronuclear shift correlation techniques has been reported. A further derivative of the constant time variable delay introduced in the IMPEACH-MBC experiment, a STAR (Selectively Tailored Accordion F(1) Refocusing) operator is described in the present report. Incorporation of the STAR operator with the capability of user-selected homonuclear modulation scaling as in the CIGAR-HMBC experiment, into a long-range heteronuclear shift correlation pulse sequence, (2)J,(3)J-HMBC, affords for the first time in a proton-detected experiment the means of unequivocally differentiating two-bond ((2)J(CH)) from three-bond ((3)J(CH)) long-range correlations to protonated carbons. Copyright 2000 Academic Press.     

1H NMR study of N(CH3)4H(ClF2CCOO)2

The proton spin–lattice relaxation times and ¹H NMR second moments were measured over a wide range of temperature. The results were compared with those of the ¹⁹F NMR relaxation that we obtained earlier. For both nuclear species, the evolution of the longitudinal magnetizations with time is observed to be strongly bi-exponential and were in good quantitative agreement with the cross-relaxation theory.