We describe a method for computing density functional energies and test it on a variety of organic and inorganic molecules. Instead of avoiding double-counting by introducing Becke weights at each point in space, we use a Hirshfeld partition of the electron density and then apply the Inclusion-Exclusion Principle to expand the energy E in a series. We find that the first term E1 contributes 95%-100% of E and that E2 delivers most of the remainder. The higher terms, E3 and E4, are generally much smaller although, in highly crowded systems such as cubane, their contribution can approach 1% of E. We propose an efficient Double Exponential + Lebedev quadrature scheme for calculating E1 and a less optimized product scheme for calculating E2 in prolate spheroidal coordinates.

The central objective of democratic governance of intelligence is, through debate and law, to establish public confidence that the agencies work efficiently, effectively and properly. Oversight of intelligence can be seen as a contest between agencies, government and overseers for the control of information. The four interacting dimensions of information control are secrecy, gathering, evaluation and persuasion. This article assesses the oversight performance of the Intelligence and Security Committee (ISC) through the prism of information control in investigating the allegations of UK involvement in torture since 2001. Operating within an overall context of executive dominance, these dimensions constitute a series of filters including what officers tell their managers, what the agencies record, what they tell ministers, what they tell oversight bodies and, finally, what the ISC reports to the public.

We define a significant shell pair in an electronic structure calculation as one that generates at least one two-electron integral larger than a preset threshold. We define a significant shell quartet similarly. We then explore several methods for identifying nonsignificant pairs and quartets so that they can be avoided and computational efficiency improved. We find that the widely used Cauchy-Schwarz bound identifies most nonsignificant quartets but that the Hölder bound is slightly more powerful for identifying nonsignificant pairs.

AbstractScience should reject all forms of censorship and defend the core principle of science – the free exchange of ideas.

This article summarizes technical advances contained in the fifth major release of the Q-Chem quantum chemistry program package, covering developments since 2015. A comprehensive library of exchange-correlation functionals, along with a suite of correlated many-body methods, continues to be a hallmark of the Q-Chem software. The many-body methods include novel variants of both coupled-cluster and configuration-interaction approaches along with methods based on the algebraic diagrammatic construction and variational reduced density-matrix methods. Methods highlighted in Q-Chem 5 include a suite of tools for modeling core-level spectroscopy, methods for describing metastable resonances, methods for computing vibronic spectra, the nuclear-electronic orbital method, and several different energy decomposition analysis techniques. High-performance capabilities including multithreaded parallelism and support for calculations on graphics processing units are described. Q-Chem boasts a community of well over 100 active academic developers, and the continuing evolution of the software is supported by an "open teamware" model and an increasingly modular design.

A major theme of the security intelligence debate in Canada has been the perceived need to find some balance between the security requirements of the state and nation on the one hand and the civil rights and liberties of individuals on the other. Some progress towards being able to judge the effectiveness of security intelligence arrangements in Canada was made with the passage of the Canadian Security Intelligence Service Act 1984. The chapter briefly discusses main contributions, categorized as those emphasizing propriety, those emphasizing efficacy and those seeming to emphasize both equally. It describes the relationship between efficacy and propriety. The statutory framework established in Canada is deficient in one central respect, that is, its coverage is limited to just one security intelligence agency and therefore assists neither the internal coordination nor the external control of that community.

This article examines the experience of oversight during the last fifty years in order to inform current debates in both the older and newer democracies. First, there is a discussion of certain key concepts: intelligence governance including control, authorisation and oversight; second, the difficulties facing oversight, specifically, how these can be alleviated by a structure involving both parliamentary and specialist bodies and, third, the challenges presented by the structures of surveillance corporatism and its reliance on bulk collection. It is concluded that this new intelligence architecture requires a form of decentred regulation of and by state and corporate actors.

As this special issue of Intelligence and National Security on 'Developing Intelligence Theory' is published, it is a decade since its three editors decided to put together an initial volume presenting the current state of conceptual thinking about intelligence. Stephen Marrin provides an evaluative review of the theoretical literature on intelligence that has been published since the Intelligence Theory volume. Comparative analysis should not be just spatial but also temporal: intelligence has been a presence in almost all societies, ancient and modern. From early democratic orders to the contemporary liberal–democratic state; one question that prompted early contributors to the academic literature on intelligence was that of the impact of intelligence practice on liberal–democratic politics. Brantly notes: '… intelligence analysis is at the dawning of a new era, a digital era in which information collected from everything from toasters and coffeemakers can now be incorporated with human sources'.

We present a quadrature-based algorithm for computing the opposite-spin component of the MP2 correlation energy which scales quadratically with basis set size and is well-suited to large-scale parallelization. The key ideas, which are rooted in the earlier work of Hirata and co-workers, are to abandon all two-electron integrals, recast the energy as a seven-dimensional integral, approximate that integral by quadrature, and employ a cutoff strategy to minimize the number of intermediate quantities. We discuss our implementation in detail and show that it parallelizes almost perfectly on 840 cores for cyclosporine (a molecule with roughly 200 atoms), exhibits [Formula: see text] scaling for a sequence of polyglycines, and is principally limited by the accuracy of its quadrature.

In the present study, we have gathered a collection (that we term TMC151) of accurate reference data for transition-metal reactions for the assessment of quantum chemistry methods. It comprises diatomic dissociation energies and reaction energies and barriers for prototypical transition-metal reactions. Our assessment of a diverse range of different types of DFT methods shows that the most accurate functionals include ωB97M-V, ωB97X-V, MN15, and B97M-rV. Notably, they have also been previously validated to be highly robust for main-group chemistry. Nevertheless, even these methods show substantially worse accuracies for transition metals than for main-group chemistry. For less accurate methods, there is not a good correlation between their accuracies for main-group and transition-metal chemistries. Thus, in the development of new DFT, it is important to assess the accuracies for both types of data. In this regard, we have formulated the TMC34 model for efficient assessment of the performance for transition metals, which complements our previously developed MG8 model for main-group chemistry. Together, they provide a cost-effective means for initial assessment of new methodologies.

ADVERTISEMENT RETURN TO ISSUESpecial Issue Prefac...Special Issue PrefaceNEXTTribute to Leo RadomAmir KartonAmir KartonMore by Amir Kartonhttp://orcid.org/0000-0002-7981-508X, Jan M. L. MartinJan M. L. MartinMore by Jan M. L. Martinhttp://orcid.org/0000-0002-0005-5074, and Peter M. W. GillPeter M. W. GillMore by Peter M. W. Gillhttp://orcid.org/0000-0003-1042-6331Cite this: J. Phys. Chem. A 2019, 123, 48, 10347Publication Date (Web):December 5, 2019Publication History Published online5 December 2019Published inissue 5 December 2019https://doi.org/10.1021/acs.jpca.9b10244Copyright © 2019 American Chemical SocietyRIGHTS & PERMISSIONSArticle Views376Altmetric-Citations-LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (1 MB) Get e-AlertsSupporting Info (1)»Supporting Information Supporting Information SUBJECTS:Computational modeling,Physical chemistry,Quality management,Students,Theoretical and computational chemistry Get e-Alerts

Species conservation depends on robust population assessment. Data on population abundance, distribution, and connectivity are critical for effective management, especially as baseline information for newly documented populations. We describe a pygmy blue whale Balaenoptera musculus brevicauda population in New Zealand waters with year-round presence that overlaps with industrial activities. This population was investigated using a multidisciplinary approach, including analysis of survey data, sighting records, acoustic data, identification photographs, and genetic samples. Blue whales were reported during every month of the year in the New Zealand Exclusive Economic Zone, with reports concentrated in the South Taranaki Bight (STB) region, where foraging behavior was frequently observed. Five hydrophones in the STB recorded the New Zealand blue whale call type on 99.7% of recording days (January to December 2016). A total of 151 individuals were photo-identified between 2004 and 2017. Nine individuals were resighted across multiple years. No matches were made to individuals identified in Australian or Antarctic waters. Mitochondrial DNA haplotype frequencies differed significantly between New Zealand (n = 53 individuals) and all other Southern Hemisphere blue whale populations, and haplotype diversity was significantly lower than all other populations. These results suggest a high degree of isolation of this New Zealand population. Using a closed capture-recapture population model, our conservative abundance estimate of blue whales in New Zealand is 718 (SD = 433, 95% CI = 279-1926). Our results fill critical knowledge gaps to improve management of blue whale populations in New Zealand and surrounding regions.

This article considers the state of play with respect to modelling and explaining intelligence. First, there are some brief comments on the issue of theory itself; second, there is a more detailed consideration of the key elements of the information and power processes which constitute 'intelligence' and, third, it examines the main variables of regime, strategy and technology that must be considered in explaining the nature of intelligence systems. Finally, some implications for future research are considered.

We present a single-determinant approach to three challenging topics in the chemistry of excited states: double excitations, charge-transfer states, and conical intersections. The results are obtained by using the Initial Maximum Overlap Method (IMOM) which is a modified version of the Maximum Overlap Method (MOM). The new algorithm converges better than the original, especially for these difficult problems. By considering several case studies, we show that a single-determinant framework provides a simple and accurate alternative for modeling excited states in cases where other low-cost methods, such as CIS and TD-DFT, either perform poorly or fail completely.

Effective core potential (ECP) integrals are among the most difficult one-electron integrals to calculate due to the projection operators. The radial part of these operators may include r0, r-1, and r-2 terms. For the r0 terms, we exploit a simple analytic expression for the fundamental projected integral to derive new recurrence relations and upper bounds for ECP integrals. For the r-1 and r-2 terms, we present a reconstruction method that replaces these terms by a sum of r0 terms and show that the resulting errors are chemically insignificant for a range of molecular properties. The new algorithm is available in Q-Chem 5.0 and is significantly faster than the ECP implementations in Q-Chem 4.4, GAMESS (US) and Dalton 2016.

How many electrons are excited in an electronic transition? In this Letter, we introduce the excitation number η to answer this question when the initial and final states are each modeled by a single-determinant wave function. We show that calculated η values lie close to positive integers, leading to unambiguous assignments of the number of excited electrons. This contrasts with previous definitions of excitation quantities which can lead to mis-assignments. We consider several examples where η provides improved excited-state characterizations.