Experimentation with different thermodynamic cycles used for pKa calculations on carboxylic acids using Complete Basis Set and Gaussian-n Models combined with CPCM Continuum Solvation Methods

Complete basis set and Gaussian-n methods were combined with Barone and Cossi's implementation of the polarizable conductor model (CPCM) continuum solvation methods to calculate pKa values for six carboxylic acids. Four different thermodynamic cycles were considered in this work. An experimental value of −264.61 kcal/mol for the free energy of solvation of H+, ΔGs(H+), was combined with a value for Ggas(H+) of −6.28 kcal/mol, to calculate pKa values with cycle 1. The complete basis set gas-phase methods used to calculate gas-phase free energies are very accurate, with mean unsigned errors of 0.3 kcal/mol and standard deviations of 0.4 kcal/mol. The CPCM solvation calculations used to calculate condensed-phase free energies are slightly less accurate than the gas-phase models, and the best method has a mean unsigned error and standard deviation of 0.4 and 0.5 kcal/mol, respectively. Thermodynamic cycles that include an explicit water in the cycle are not accurate when the free energy of solvation of a water molecule is used, but appear to become accurate when the experimental free energy of vaporization of water is used. This apparent improvement is an artifact of the standard state used in the calculation. Geometry relaxation in solution does not improve the results when using these later cycles. The use of cycle 1 and the complete basis set models combined with the CPCM solvation methods yielded pKa values accurate to less than half a pKa unit. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem, 2001

Accurate pKa Calculations for Carboxylic Acids Using Complete Basis Set and Gaussian-n Models Combined with CPCM Continuum Solvation Methods”

Complete Basis Set and Gaussian-n methods were combined with CPCM continuum solvation methods to calculate pKa values for six carboxylic acids. An experimental value of −264.61 kcal/mol for the free energy of solvation of H+, ΔGs(H+), was combined with a value for Ggas(H+) of −6.28 kcal/mol to calculate pKa values with Cycle 1. The Complete Basis Set gas-phase methods used to calculate gas-phase free energies are very accurate, with mean unsigned errors of 0.3 kcal/mol and standard deviations of 0.4 kcal/mol. The CPCM solvation calculations used to calculate condensed-phase free energies are slightly less accurate than the gas-phase models, and the best method has a mean unsigned error and standard deviation of 0.4 and 0.5 kcal/mol, respectively. The use of Cycle 1 and the Complete Basis Set models combined with the CPCM solvation methods yielded pKa values accurate to less than half a pKa unit.

Human Resource Performance Metrics: Methods & Processes That Demonstrate You Care

Purpose – The purpose of the present analysis is to show that HR systems are not always designed in ways that consider the well-being of employees. In particular, performance metric methods seem to be designed with organizational goals in mind while focusing less on what employees need and desire. Design/methodology/approach – A literature review and multiple case-study method was utilized. Findings – The analysis showed that performance metrics should be revaluated by executives and HR professionals if they seek to develop socially responsible organizational cultures which care about the well-being of employees. Originality/value – The paper exposes the fact that performance appraisal techniques can be rooted in methodologies that ignore or deemphasize the value of employee well-being. The analysis provides a context in which all HR practices can be questioned in relation to meeting the standards of a social justice agenda in the area of corporate social responsibility.

Mother-Child Spiritual Discourse: A Mixed Methods Study

Parents and children, starting at very young ages, discuss religious and spiritual issues¿where we come from, what happens to us after we die, is there a God, and so on. Unfortunately, few studies have analyzed the content and structure of parent-child conversation about religion and spirituality (Boyatzis & Janicki, 2003; Dollahite & Thatcher, 2009), and most studies have relied on self-report with no direct observation. The current study examined mother-child (M-C) spiritual discourse to learn about its content, structure, and frequency through a survey inventory in combination with direct video observation using a novel structured task. We also analyzed how mothers¿ religiosity along several major dimensions related to their communication behaviors within both methods. Mothers (N = 39, M age = 40) of children aged 3-12 completed a survey packet on M-C spiritual discourse and standard measures of mothers¿ religious fundamentalism, intrinsic religiosity, sanctification of parenting (how much the mother saw herself as doing God¿s work as a parent), and a new measure of parental openness to children¿s spirituality. Then, in a structured task in our lab, mothers (N = 33) and children (M age = 7.33) watched a short film or read a short book that explored death in an age-appropriate manner and then engaged in a videotaped conversation about the movie or book and their religious or spiritual beliefs. Frequency of M-C spiritual discourse was positively related to mothers¿ religious fundamentalism (r = .71, p = .00), intrinsic religiosity (r = .77, p = .00), and sanctification of parenting (r = .79, p = .00), but, surprisingly, was inversely related to mothers¿ v openness to child¿s spirituality (r = -.52, p = .00). Survey data showed that the two most common topics discussed were God (once a week) and religion as it relates to moral issues (once a week). According to mothers their children¿s most common method of initiating spiritual discourse was to repeat what he or she has heard parents or family say about religious issues (M = 2.97; once a week); mothers¿ most common method was to describe their own religious/spiritual beliefs (M = 2.92). Spiritual discourse most commonly occurred either at bedtime or mealtime as reported by 26% of mothers, with the most common triggers reported as daily routine/random thoughts (once a week) and observations of nature (once a week). Mothers¿ most important goals for spiritual discourse were to let their children know that they love them (M = 3.72; very important) and to help them become a good and moral person (M = 3.67; very important). A regression model showed that significant variance in frequency of mother-child spiritual discourse (R2 = .84, p = .00) was predicted by the mothers¿ importance of goals during discourse (ß = 0.46, p = .00), frequency that the mother¿s spirituality was deepened through spiritual discourse (ß = 0.39, p = .00), and the mother¿s fundamentalism (ß = 0.20, p = .05). In a separate regression, the mother¿s comfort in the structured task (ß = 0.70, p = .00), and the number of open-ended questions she asked (ß = -0.26, p = .03) predicted the reciprocity between mother and child (R2 = .62, p = .00). In addition, the mother¿s age (ß = 0.22, p = .059) and comfort during the task (ß = 0.73, p = .00) predicted the child¿s engagement within the structured task. Other findings and theoretical and methodological implications will be discussed.

Coping With a Family Member's Death: Parenting, Religiosity, and Parent-Child Communication

The present study had three major aims. First, this study was a basic descriptive exploration of the frequency and nature of parent-child communication about death. Second, this study conducted a quantitative analysis to identify predictors of communication and bereaved children¿s emotional and behavioral problems. Third, this study was also a qualitative analysis of parents¿ descriptions of how religious views shape conversations about death and how conversations are beneficial. Based on prior research, it was predicted that positive child outcomes would be associated with parental warmth, religiosity, adaptive coping, positive religious coping, and frequent parent-child communication about death. Conversely, it was predicted that negative child outcomes would be associated with parental psychological control, maladaptive coping, negative religious coping, and less frequent parent-child communication about death. Additionally, it was hypothesized that parents¿ religious and spiritual views would shape parent-child communication about death, and parents would describe numerous benefits of discussing death with children. Parents completed a series of survey measures assessing their religiosity, coping strategies, parent-child communication about death, and their children¿s emotional and behavioral symptoms. Almost 80% of parent-child dyads discussed death at least once a week, and children initiated approximately half of these conversations. Parent-child communication about death was predicted by parents¿ warmth toward and acceptance of their children and inversely predicted by children¿s hyperactivity and social problem solving. Higher levels of children¿s social problem solving could predict lower frequency of parent-child communication about death if children were holding frequent, meaningful, and comforting conversations with friends and other adults. Higher levels of parents¿ psychological control predicted more emotional and behavioral problems in the child. Parents¿ adaptive coping had significant relationships with all of the dimensions of parent-child communication about death. Qualitative analyses revealed that parents perceived their religious beliefs as shaping conversations about death and grief as an individualized journey. A majority of parents described the emotional, social, and intellectual benefits of holding parent-child conversations about death. This study contributes to the literature by further describing parent-child communication about death, identifying its predictors, and investigating parents¿ religiosity and coping strategies in relation to child well-being. Overall, this study revealed the importance of assessing global parenting characteristics (i.e., warmth/acceptance and psychological control) when examining parent-child relationships and communication about death. Furthermore, this unique study illustrates the value of qualitative data when examining parent-child communication about death and religiosity.