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We derive equations for describing the time evolution of variational wave functions in linear and exponential parameterization with a second-quantization (SQ) formulation. The SQ formalism covers time-dependent Hartree (TDH), while exact states and approximate vibrational configuration interaction wave functions are described using state-transfer operators. We present detailed expressions for efficient evaluation of TDH in linear (L-TDH) and exponential (X-TDH) parametrization and an efficient implementation supporting linear scaling with respect to the number of degrees of freedom M when the Hamiltonian operator contains a constant number of terms per mode independently of the size of the system. The computational cost of the X-TDH method is reduced significantly compared to the L-TDH method for systems with many operator terms per mode such as is typical for accurate molecular potential-energy surfaces. Numerical results for L-TDH and X-TDH are presented which confirm the theoretical reduction of the M scaling compared to standard first-quantization formulations. Calculations on Henon-Heiles potentials with more than 105 dimensions and polycyclic aromatic hydrocarbons with up to 264 modes have been performed. Thus, the SQ formulation and the X-TDH method pave the way for studying the time-resolved quantum dynamics of large molecules. [ABSTRACT FROM AUTHOR]

Background We studied the effects of endovascular treatment (EVT) and the impact of the extent of recanalization on cerebral perfusion and oxygenation parameters in patients with acute ischemic stroke (AIS) and large vessel occlusion (LVO). Methods Forty-seven patients with anterior LVO underwent computed tomography perfusion (CTP) before and immediately after EVT. The entire ischemic region (Tmax >6 s) was segmented before intervention, and tissue perfusion (time-to-maximum (Tmax), time-to-peak (TTP), mean transit time (MTT), cerebral blood volume (CBV), cerebral blood flow (CBF)) and oxygenation (coefficient of variation (COV), capillary transit time heterogeneity (CTH), metabolic rate of oxygen (CMRO2), oxygen extraction fraction (OEF)) parameters were quantified from the segmented area at baseline and the corresponding area immediately after intervention, as well as within the ischemic core and penumbra. The impact of the extent of recanalization (modified Treatment in Cerebral Infarction (mTICI)) on CTP parameters was assessed with the Wilcoxon test and Pearson's correlation coefficients. Results The Tmax, MTT, OEF and CTH values immediately after EVT were lower in patients with complete (as compared with incomplete) recanalization, whereas CBF and COV values were higher (P<0.05) and no differences were found in other parameters. The ischemic penumbra immediately after EVT was lower in patients with complete recanalization as compared with those with incomplete recanalization (P=0.002), whereas no difference was found for the ischemic core (P=0.12). Specifically, higher mTICI scores were associated with a greater reduction of ischemic penumbra volumes (R²=-0.48 (95% CI -0.67 to -0.22), P=0.001) but not of ischemic core volumes (P=0.098). Conclusions Our study demonstrates that the ischemic penumbra is the key target of successful EVT in patients with AIS and largely determines its efficacy on a tissue level. Furthermore, we confirm the validity of the mTICI score as a surrogate parameter of interventional success on a tissue perfusion level. [ABSTRACT FROM AUTHOR]

The vibrational coupled cluster (VCC) equations are analyzed in terms of vibrational Mo\ller-Plesset perturbation theory aiming specifically at the importance of four-mode couplings. Based on this analysis, new VCC methods are derived for the calculation of anharmonic vibrational energies and vibrational spectra using vibrational coupled cluster response theory. It is shown how the effect of four-mode coupling and excitations can be efficiently and accurately described using approximations for their inclusion. Two closely related approaches are suggested. The computational scaling of the so-called VCC[3pt4F] method is not higher than the fifth power in the number of vibrational degrees of freedom when up to four-mode coupling terms are present in the Hamiltonian and only fourth order when only up to three-mode couplings are present. With a further approximation, one obtains the VCC[3pt4] model which is shown to scale with at most the fourth power in the number of vibrational degrees of freedom for Hamiltonians with both three- and four-mode coupling levels, while sharing the most important characteristics with VCC[3pt4F]. Sample calculations reported for selected tetra-atomic molecules as well as the larger dioxirane and ethylene oxide molecules support that the new models are accurate and useful. [ABSTRACT FROM AUTHOR]

We report the theory and implementation of vibrational coupled cluster (VCC) damped response functions. From the imaginary part of the damped VCC response function the absorption as function of frequency can be obtained, requiring formally the solution of the now complex VCC response equations. The absorption spectrum can in this formulation be seen as a matrix function of the characteristic VCC Jacobian response matrix. The asymmetric matrix version of the Lanczos method is used to generate a tridiagonal representation of the VCC response Jacobian. Solving the complex response equations in the relevant Lanczos space provides a method for calculating the VCC damped response functions and thereby subsequently the absorption spectra. The convergence behaviour of the algorithm is discussed theoretically and tested for different levels of completeness of the VCC expansion. Comparison is made with results from the recently reported [P. Seidler, M. B. Hansen, W. Györffy, D. Toffoli, and O. Christiansen, J. Chem. Phys. 132, 164105 (2010)] vibrational configuration interaction damped response function calculated using a symmetric Lanczos algorithm. Calculations of IR spectra of oxazole, cyclopropene, and uracil illustrate the usefulness of the new VCC based method. [ABSTRACT FROM AUTHOR]

In continuation of our recent paper on vibrational quadratic response functions for vibrational configuration interaction wave functions, we present in this paper a derivation and implementation of the pure vibrational cubic response function for vibrational configuration interaction wave functions. In addition, we present combined electronic and vibrational cubic response functions derived from sum-over-states expressions in the Born-Oppenheimer framework and a discussion of complicating issues. The implementation enables analytic calculation of the pure vibrational cubic response function via response theory, which constitutes a part of the vibronic cubic response function. [ABSTRACT FROM AUTHOR]

We present an approach based on the Lanczos method for calculating the vibrational configuration interaction response functions necessary for evaluating the pure vibrational contributions to the polarizabilities and first hyperpolarizabilities of molecules. The method iteratively builds a tridiagonal representation of the central response matrix, which is subsequently used for solving the response equations. From the same chain, the response functions can be evaluated approximately for any frequency as well as using any complex damping factor. Applications to formaldehyde, cyclopropene, and uracil illustrate the concepts presented. [ABSTRACT FROM AUTHOR]

The Lanczos method is used to efficiently obtain the linear vibrational response function for all frequencies in an arbitrary interval. The complex part of the response function gives the absorption spectrum which can subsequently be analyzed. The method provides a way to obtain global information on the absorption spectrum without explicitly converging all vibrational eigenstates of the system. The tridiagonal Lanczos matrix used to obtain the response functions needs only be constructed once for each operator. Example calculations on cyclopropene and uracil are presented. [ABSTRACT FROM AUTHOR]

Quadratic response functions are derived and implemented for a vibrational configuration interaction state. Combined electronic and vibrational quadratic response functions are derived using Born–Oppenheimer vibronic product wave functions. Computational tractable expressions are derived for determining the total quadratic response contribution as a sum of contributions involving both electronic and vibrational linear and quadratic response functions. In the general frequency-dependent case this includes a new and more troublesome type of electronic linear response function. Pilot calculations for the FH, H2O, CH2O, and pyrrole molecules demonstrate the importance of vibrational contributions for accurate comparison to experiment and that the vibrational contributions in some cases can be very large. The calculation of transition properties between vibrational states is combined with sum-over-states expressions for analysis purposes. On the basis of this some simple analysis methods are suggested. Also, a preliminary study of the effect of finite lifetimes on quadratic response functions is presented. [ABSTRACT FROM AUTHOR]

A new method is described for the calculation of molecular vibrational partition functions and thermal effects on molecular properties including an explicit account of anharmonicity. The approach is based on the vibrational self-consistent-field method. Partition functions and thermal averages of the energies calculated with the new method are generally in good agreement with the result of more accurate methods. At lower temperatures the method gives in addition good results for thermal averages of dipole moments and polarizabilities. The new method is much more efficient than explicit sum-over-states approaches previously used for calculation of thermal averages. Unlike the standard sum-over-states approach, the newly developed method is feasible for larger systems despite the formal exponential increase in the number of states with the size of the system. Thus, it is presently the only practical way for including an explicit treatment of anharmonicity in vibrational wave function based calculations of molecular vibrational partition functions and thermally averaged properties of larger molecules. [ABSTRACT FROM AUTHOR]

An efficient implementation of vibrational coupled cluster theory with two-mode excitations and a two-mode Hamiltonian is described. The algorithm is shown to scale cubically with respect to the number of modes which is identical to the scaling of the corresponding vibrational configuration interaction algorithm. This is achieved through the use of special intermediates. The same algorithm can also be used in vibrational Mo\ller–Plesset calculations. To improve performance, screening techniques have been implemented as well. Test calculations on polyaromatic hydrocarbons with up to 264 coupled modes and model systems with up to 1140 modes are used to illustrate the various features of the algorithm. [ABSTRACT FROM AUTHOR]

Purpose: To present and quantify the performance of a method to compute tissue hemodynamic parameters from dynamic susceptibility contrast (DSC) MRI data in brain tissue with possible nonintact blood-brain barrier., Theory and Materials and Methods: We propose a Bayesian scheme to obtain perfusion metrics, including capillary transit-time heterogeneity (CTH), from DSC-MRI data in the presence of contrast agent extravasation. Initial performance assessment is performed through simulations. Next, we assessed possible over- or under correction for tracer extravasation in two patients receiving contrast agent preloading and two patients not receiving preloading. Perfusion metrics for N = 60 patients diagnosed with either grade III (N = 14) or grade IV gliomas (N = 46) were analyzed across tissue types to evaluate the ability to distinguish regions with different hemodynamic patterns. Finally, N = 4 patient cases undergoing anti-angiogenic treatment are evaluated qualitatively for treatment effects. All patient data were acquired at 3.0 Tesla., Results: The simulation studies showed good robustness against low signal-to-noise ratios, exemplified with Pearson correlations of R = 0.833 (mean transit time) and R = 0.738 (CTH) at signal-to-noise ratio = 20. Region-of-interest analysis of the N = 60 glioma patients showed that cerebral blood volume (CBV) significantly separated enhancing core from edema (grade IV: P < 10 -8 , grade III: P < 0.05) and enhancing core from normal appearing ipsilateral white matter (NAWM) (grade IV: P < 10 -8 , grade III: P < 0.05). The microvascular parameters were particularly good in separating edematous tissue from NAWM tissue in grade IV gliomas (P < 0.001). Finally, CTH separated grade III and grade IV core tissue (P < 0.05)., Conclusion: We have demonstrated robustness of the proposed Bayesian algorithm against experimental noise and demonstrated complementary value in microvascular parameters to the CBV parameter in separating tissue types in gliomas., Level of Evidence: 3 Technical Efficacy: Stage 2 J. MAGN. RESON. IMAGING 2017;46:537-549., (© 2016 International Society for Magnetic Resonance in Medicine.)