title: Explicitly correlated intermolecular distances and interaction energies of hydrogen bonded complexes

authors: Lane, Joseph R.

subjects: chemistry

abstract: We have optimized the lowest energy structures and calculated interaction energies for the H2O–H2O, H2O–H2S, H2O–NH3, and H2O–PH3 dimers with the recently developed explicitly correlated CCSD(T)-F12 methods and the associated VXZ-F12 (where X=D,T,Q) basis sets. For a given cardinal number, we find that the results obtained with the CCSD(T)-F12 methods are much closer to the CCSD(T) complete basis set limit than the conventional CCSD(T) results. In general we find that CCSD(T)-F12 results obtained with the VTZ-F12 basis set are better than the conventional CCSD(T) results obtained with an aug-cc-pV5Z basis set. We also investigate two ways to reduce the effects of basis set superposition error with conventional CCSD(T), namely, the popular counterpoise correction and limiting diffuse basis functions to the heavy atoms only. We find that for a given cardinal number, these selectively augmented correlation consistent basis sets yield results that are closer to the complete basis set limit than the corresponding fully augmented basis sets. Furthermore, we find that the difference between standard and counterpoise corrected interaction energies and intermolecular distances is reduced with the selectively augmented basis sets.

text: Explicitly correlated intermolecular distances and interaction energies of hydrogen bonded complexes We have optimized the lowest energy structures and calculated interaction energies for the H2O–H2O, H2O–H2S, H2O–NH3, and H2O–PH3 dimers with the recently developed explicitly correlated CCSD(T)-F12 methods and the associated VXZ-F12 (where X=D,T,Q) basis sets. For a given cardinal number, we find that the results obtained with the CCSD(T)-F12 methods are much closer to the CCSD(T) complete basis set limit than the conventional CCSD(T) results. In general we find that CCSD(T)-F12 results obtained with the VTZ-F12 basis set are better than the conventional CCSD(T) results obtained with an aug-cc-pV5Z basis set. We also investigate two ways to reduce the effects of basis set superposition error with conventional CCSD(T), namely, the popular counterpoise correction and limiting diffuse basis functions to the heavy atoms only. We find that for a given cardinal number, these selectively augmented correlation consistent basis sets yield results that are closer to the complete basis set limit than the corresponding fully augmented basis sets. Furthermore, we find that the difference between standard and counterpoise corrected interaction energies and intermolecular distances is reduced with the selectively augmented basis sets.

year: 2009

title: Living with the Aftermath of Male Child Sexual Abuse

authors: Coveny, Doris

subjects: Child sexual abuse

abstract: Child sexual abuse (CSA) in boys has been shown to have long lasting and devastating effects on men's lives. Negative health outcomes such as anxiety, posttraumatic stress disorder, depression, poor social skills, destructive lifestyles, and mistrust towards others are only a few of the reported after-effects. Research of CSA is largely focused on girls and women, leaving a relative shortage on men. This qualitative study attempts to add to the dearth of literature in this field by reporting findings from narrative interviews with men who were sexually abused as children. The aim was to investigate how men reconciled their early experiences of CSA with everyday life and their relationships with others. Seven participants of New Zealand European and one participant of Māori descent participated in a loosely structured conversational interview. The study was guided by narrative theory and social constructionist epistemology using thematic narrative analysis to interpret the data. The findings are discussed within seven overarching themes: Shame, guilt, and lost self-identities illustrates how survivors of CSA can become very isolated due to their internalised feelings of inferiority and self-blame.  The participants' inability to share their experiences alienated them from others as much as themselves, which ultimately affected their sense of belonging. CSA instilled feelings of self-loathing and inadequacy as well as it fostered low self-esteem and led to the loss of their self-identity. Anger and hurt - a kind of death/an empty shell highlights the expression of heightened anger resulting from their experiences and isolation. Participants appeared confused, lost and empty without aspirations or hopes for the future. It describes a long process of regaining meaning in life, which some men found in fatherhood despite its challenges. Escaping the pain describes the men's emotional and physical turmoil, which triggered attempts to forget past events. Many participants engaged in violence and substance use, tried to become someone else, or end their life. Damage boils over talks about the participants' memories of their CSA experiences and the associated effects on their daily lives. It demonstrates how CSA can affect men's emotional stability and reactions when situations become too distressing. Mistrust - a place of safety summarises participants' feelings of mistrust towards others and their difficulty to accept forms of authority. It highlights CSA's potential aftermath in regards to interpersonal and romantic relationships as well as over protectiveness towards children.  Social norms and barriers to disclosure discusses the difficulties surrounding disclosure of CSA, spanning both childhood and adulthood. Further, it shows how social norms such as hegemonic masculinity can influence outcomes. From missed opportunities to healing describes regrets about perceived undeveloped talents, educational opportunities, or loss of family. The theme shows how coping mechanisms helped to navigate life and describes the benefits of counselling.

text: Living with the Aftermath of Male Child Sexual Abuse Child sexual abuse (CSA) in boys has been shown to have long lasting and devastating effects on men's lives. Negative health outcomes such as anxiety, posttraumatic stress disorder, depression, poor social skills, destructive lifestyles, and mistrust towards others are only a few of the reported after-effects. Research of CSA is largely focused on girls and women, leaving a relative shortage on men. This qualitative study attempts to add to the dearth of literature in this field by reporting findings from narrative interviews with men who were sexually abused as children. The aim was to investigate how men reconciled their early experiences of CSA with everyday life and their relationships with others. Seven participants of New Zealand European and one participant of Māori descent participated in a loosely structured conversational interview. The study was guided by narrative theory and social constructionist epistemology using thematic narrative analysis to interpret the data. The findings are discussed within seven overarching themes: Shame, guilt, and lost self-identities illustrates how survivors of CSA can become very isolated due to their internalised feelings of inferiority and self-blame.  The participants' inability to share their experiences alienated them from others as much as themselves, which ultimately affected their sense of belonging. CSA instilled feelings of self-loathing and inadequacy as well as it fostered low self-esteem and led to the loss of their self-identity. Anger and hurt - a kind of death/an empty shell highlights the expression of heightened anger resulting from their experiences and isolation. Participants appeared confused, lost and empty without aspirations or hopes for the future. It describes a long process of regaining meaning in life, which some men found in fatherhood despite its challenges. Escaping the pain describes the men's emotional and physical turmoil, which triggered attempts to forget past events. Many participants engaged in violence and substance use, tried to become someone else, or end their life. Damage boils over talks about the participants' memories of their CSA experiences and the associated effects on their daily lives. It demonstrates how CSA can affect men's emotional stability and reactions when situations become too distressing. Mistrust - a place of safety summarises participants' feelings of mistrust towards others and their difficulty to accept forms of authority. It highlights CSA's potential aftermath in regards to interpersonal and romantic relationships as well as over protectiveness towards children.  Social norms and barriers to disclosure discusses the difficulties surrounding disclosure of CSA, spanning both childhood and adulthood. Further, it shows how social norms such as hegemonic masculinity can influence outcomes. From missed opportunities to healing describes regrets about perceived undeveloped talents, educational opportunities, or loss of family. The theme shows how coping mechanisms helped to navigate life and describes the benefits of counselling.

year: 2017

title: Beyond structuralism: Exploring a semantic based approach for describing the Māori language in grammar books and textbooks for pedagogical purposes

authors: Taiapa, Michael William

subjects: Māori

abstract: Since the 1950s, the advancements and developments in English language studies has had a profound impact on its description that has made it less syntactically driven and more communicatively oriented. This has the potential to influence language description moving it from a purely structurally focused orientation to a more semantically focused one that could influence pedagogic outcomes in more meaningful and useful ways. Nevertheless, in the case of the Māori language, its description has largely focused on structure linguistics that was prevalent in the 19th and early 20th centuries. There has been very little focus on a semantic description and this, in turn, is reflected in grammar books and textbooks on te reo. This thesis set out to explore a semantic approach to describe te reo and to rethink how this type of description may be realized and included in the design of grammar books and textbooks for the teaching and learning of te reo in the broader field of second language pedagogy and acquisition. The thesis also includes a practical component in which a small sample of Māori language teachers were interviewed to determine how linguistic and/ or semantic approaches to describe te reo may have or have impacted on their own beliefs, attitudes, and teaching practices (See, Chapter 7). Thus, it is argued here that research-based studies, advancements, and developments in language descriptions over the past five decades (See, for example, Council of Europe, 1949; Fillmore, 1967; Longacre, 1968; & Crombie, 1985b) should play central roles in the design of a semantic based description of the Māori language from which a linguistic based description can significantly benefit.

text: Beyond structuralism: Exploring a semantic based approach for describing the Māori language in grammar books and textbooks for pedagogical purposes Since the 1950s, the advancements and developments in English language studies has had a profound impact on its description that has made it less syntactically driven and more communicatively oriented. This has the potential to influence language description moving it from a purely structurally focused orientation to a more semantically focused one that could influence pedagogic outcomes in more meaningful and useful ways. Nevertheless, in the case of the Māori language, its description has largely focused on structure linguistics that was prevalent in the 19th and early 20th centuries. There has been very little focus on a semantic description and this, in turn, is reflected in grammar books and textbooks on te reo. This thesis set out to explore a semantic approach to describe te reo and to rethink how this type of description may be realized and included in the design of grammar books and textbooks for the teaching and learning of te reo in the broader field of second language pedagogy and acquisition. The thesis also includes a practical component in which a small sample of Māori language teachers were interviewed to determine how linguistic and/ or semantic approaches to describe te reo may have or have impacted on their own beliefs, attitudes, and teaching practices (See, Chapter 7). Thus, it is argued here that research-based studies, advancements, and developments in language descriptions over the past five decades (See, for example, Council of Europe, 1949; Fillmore, 1967; Longacre, 1968; & Crombie, 1985b) should play central roles in the design of a semantic based description of the Māori language from which a linguistic based description can significantly benefit.

year: 2023