Molecular anharmonicity: A computer-aided treatment

We present a new software package for the theoretical treatment of anharmonic vibrational spectra of nonlinear polyatomic molecules. The package, called “B&D,” computes vibrational energies starting from sets of force constants defined as potential energy derivatives. The method employed allows us to combine experimental rotation-vibration data with any information made available from ab initio calculations. The package follows the natural procedure in which a molecular problem is solved, both in the symbolic construction of Hamiltonian operator and basis functions and in the numerical computation of the Hamiltonian matrix elements. The novelty consists in making the entire procedure fully automatic, so that the occurrence of errors is greatly reduced and the laborious process involved in deriving and implementing the Hamiltonian is dramatically simplified. © 1999 John Wiley & Sons, Inc. J Comput Chem 20: 1716–1730, 1999     

Thermal effects in singly resonant continuous-wave optical parametric oscillators

Stability and tuning characteristics of continuous-wave optical parametric oscillators (CW OPOs) are affected by various thermal effects arising from optical absorption in nonlinear crystals. In this paper, we present an experimental study of such effects in a singly resonant CW OPO. The OPO operates in the 3-μm mid-infrared region and it is based on a MgO-doped periodically poled lithium niobate crystal. We focus our study on two thermally induced phenomena that have been recently reported to exist in singly resonant CW OPOs: optical bi-stability and thermal self-locking. Thermal self-locking effect, which is known to alter the stability and tuning properties of doubly and triply resonant CW OPOs, is shown to be also of importance in singly resonant OPOs. We report the stability and tuning characteristics of a thermally loaded OPO and discuss a simple temperature-tuning method that can be used to scan the OPO idler frequency continuously over several THz.     

Abnormal inversion splitting in NH2D: rotational analysis of the nu5 bending vibrational band system

A high-resolution Fourier transform infrared spectrum of the nu(5) bending vibrational band system region of the partially deuterated ammonia molecule NH(2)D has been measured and rotationally analyzed. The spectrum consists of strong a-type transitions between the states of same vibrational symmetry and weaker c-type transitions between the states of different vibrational symmetry. The Hamiltonian model used includes interaction terms between the rotational states of both upper and lower inversion doublets. The vibrational term values for the symmetric and the antisymmetric component of the upper-inversion doublet are 1,605.637 965(620) cm(-1) and 1,590.993 82(100) cm(-1), respectively, where the numbers in parentheses are one-standard deviations in the least significant digit. These figures are close to the corresponding values 1,605.62 cm(-1) and 1,590.72 cm(-1) obtained recently from results based on high-level ab initio calculations. The order of the vibrational term values is abnormal in the ammonia family, as typically the symmetric state is lower in wavenumber than the antisymmetric one.     

A nine-dimensional calculation of the vibrational OH stretching and HOH bending spectrum of the water trimer

We have studied the vibrational high-frequency spectrum of the water trimer computationally. We expand an earlier study [J. Chem. Phys. A 2009, 113, 9124-9132] where we approximated the water trimer as three individually vibrating water monomer units. Some intramolecular potential energy coupling terms are now included in the previous model. The six OH bond lengths and the three HOH bending angles are used as the internal coordinates. The kinetic energy operator is a sum of the kinetic energy operators of the monomer units. We use the coupled cluster method with single, double, and perturbative triple excitations method [CCSD(T)] with augmented correlation consistent polarized valence triple-ζ (aug-cc-pVTZ) basis set to calculate the potential energy surface (PES). The counterpoise correction is included in the one-dimensional part of the PES. We calculate the vibrational energy eigenvalues using the variational method. The corresponding eigenfunctions are used to obtain the absorption intensities.     

Ab initio structural and vibrational investigation of sulfuric acid monohydrate

We employ ab initio methods to find stable geometries and to calculate potential energy surfaces and vibrational wavenumbers for sulfuric acid monohydrate. Geometry optimizations are carried out with the explicitly correlated coupled-cluster approach that includes single, double, and perturbative triple excitations (CCSD(T)-F12a) with a valence double-ζ basis set (VDZ-F12). Four different stable geometries are found, and the two lowest are within 0.41 kJ mol(-1) (or 34 cm(-1)) of each other. Vibrational harmonic wavenumbers are calculated at both the density-fitted local spin component scaled second-order M?ller-Plesset perturbation theory (DF-SCS-LMP2) with the aug-cc-pV(T+d)Z basis set and the CCSD-F12/VDZ-F12 level. Water O-H stretching vibrations and two highly anharmonic large-amplitude motions connecting the three lowest potential energy minima are considered by limiting the dimensionality of the corresponding potential energy surfaces to small two- or three-dimensional subspaces that contain only strongly coupled vibrational degrees of freedom. In these anharmonic domains, the vibrational problem is solved variationally using potential energy surfaces calculated at the CCSD(T)-F12a/VDZ-F12 level.     

2.7 V 50 MHz IF sampling ΔΣ modulator with +37 dBV IIP3

The design and experimental results of a 2.7 V 50 MHz switched-capacitor DS modulator in a 0.35 μm BiCMOS process are presented. The circuit is targeted for the IF section of a radio receiver in a GSM cellular phone. It combines frequency downconversion with analogue to digital conversion by directly sampling an input signal from an IF of 50 MHz. The measured peak signal-to-noise ratio for a 100 kHz bandwidth is 81 dB with a 53 MHz blocking signal and the measured IIP3 for IF input is +36.9 dBV     

Performance characteristics of buried heterostructure VCSELs usingsemi-insulating GaInP:Fe regrowth

We have fabricated GaAs-AlGaAs buried heterostructure vertical cavity surface emitting lasers, emitting at 850 mm, using semi-insulating GaInP:Fe regrowth and investigated their static properties. Lasers of different size (10-21 μm) have threshold currents in the range 2.8-7.0 mA, and produce a maximum output power of 1.7-6.0 mW at room temperature. The variation of threshold current with device size shows that the leakage current at the regrowth interface accounts for a significant part of the injection current. In spite of this, a differential quantum efficiency in the range 20%-30% is obtained which indicates that the regrowth interface is smooth and does not introduce any significant scattering loss. Studies of the transverse mode properties suggest that the GaInP provides weak guiding, resulting in single mode operation up to an output power of 0.7 mW and a beam divergence of only 60 for lasers as large as 10 μm     

Low-Voltage CMOS Rail-to-Rail V-I Converters

This paper presents two CMOS low-voltage rail-to-rail voltage-to-current converters (V-I converter) which could be used as basic building blocks to construct low-voltage current-mode analog VLSI circuits. In each of the circuits, an N-type V-I converter cell is connected in parallel with its P-type counterpart to achieve common-mode rail-to-rail operation. A linear differential relationship of the N-type V-I converter, or its P-type complement, is obtained using a new class-AB linearization technique. In the first rail-to-rail V-I converter circuit, a constant transconductance is achieved through the use of two maximum-current selecting circuits and an output subtraction stage. In the second circuit, a constant transconductance value is obtained by manipulating the DC bias currents of N- and P-type V-I converter cells. Both of the circuits can operate from rail to rail with a power supply of 3V, or less depending on the VLSI technology and the DC bias current level.     

A 14b 100-MS/s Time-Interleaved A/D Converter

This article presents a 14-bit, 100-MS/s time-interleaved pipeline ADC, which samples input signal from 210-MHz IF-band. Digital self-calibration is employed to compensate gain mismatch and offset between time-interleaved channels as well as mismatches arise from a single ADC channel. A timing skew-insensitive parallel S/H circuit is utilized in order to avoid timing skew between parallel ADC channels. The ADC, fabricated in a 0.35-μm BiCMOS (SiGe) takes an area of 10.2 mm², reaches an ENOB of 11.4 bits with a 79.9-dB SFDR at 192.5-MHz input and draws 1.4 W from a 3.0-V supply.     

Kinetics of the reactions of chlorinated methyl radicals (CH2Cl, CHCl2, and CCl3) with NO2 in the temperature range 220-360 K

The kinetics of the reactions of chlorinated methyl radicals (CH2Cl, CHCl2, and CCl3) with NO2 have been studied in direct measurements at temperatures between 220 and 360 K using a tubular flow reactor coupled to a photoionization mass spectrometer. The radicals have been homogeneously generated at 193 or 248 nm by pulsed laser photolysis of appropriate precursors. Decays of radical concentrations have been monitored in time-resolved measurements to obtain the reaction rate coefficients under pseudo-first-order conditions with the amount of NO2 being in large excess over radical concentrations. The bimolecular rate coefficients of all three reactions are independent of the bath gas (He or N2) and pressure within the experimental range (1-6 Torr) and are found to depend on temperature as follows: k(CH2Cl + NO2) = (2.16 +/- 0.08) x 10(-11) (T/300 K)(-1.12+/-0.24) cm3 molecule(-1) s(-1) (220-363 K), k(CHCl2 + NO2) = (8.90 +/- 0.16) x 10(-12) (T/300 K)(-1.48+/-0.13) cm3 molecule(-1) s(-1) (220-363 K), and k(CCl3 + NO2) = (3.35 +/- 0.10) x 10(-12) (T/300 K)(-2.2+/-0.4) cm3 molecule(-1) s(-1) (298-363 K), with the uncertainties given as one-standard deviations. Estimated overall uncertainties in the measured bimolecular reaction rate coefficients are about +/-25%. In the reactions CH2Cl + NO2, CHCl2 + NO2, and CCl3 + NO2, the products observed are formaldehyde, CHClO, and phosgene (CCl2O), respectively. In addition, a weak signal for the HCl formation has been detected for the CHCl2 + NO2 reaction.