Shape and chemically anisotropic colloidal particles: A theoretical study of their structure, phase behavior, and slow dynamics

A detailed non-equilibrium state diagram of shape-anisotropic particle fluids is constructed. The effects of particle shape are explored using Naive Mode Coupling Theory (NMCT), and a single particle Non-linear Langevin Equation (NLE) theory. The dynamical behavior of non-ergodic fluids are discussed. We employ a rotationally frozen approach to NMCT in order to determine a transition to center of mass (translational) localization. Both ideal and kinetic glass transitions are found to be highly shape dependent, and uniformly increase with particle dimensionality. The glass transition volume fraction of quasi 1- and 2- dimensional particles fall monotonically with the number of sites (aspect ratio), while 3-dimensional particles display a non-monotonic dependence of glassy vitrification on the number of sites. Introducing interparticle attractions results in a far more complex state diagram. The ideal non-ergodic boundary shows a glass-fluid-gel re-entrance previously predicted for spherical particle fluids. The non-ergodic region of the state diagram presents qualitatively different dynamics in different regimes. They are qualified by the different behaviors of the NLE dynamic free energy. The caging dominated, repulsive glass regime is characterized by long localization lengths and barrier locations, dictated by repulsive hard core interactions, while the bonding dominated gel region has short localization lengths (commensurate with the attraction range), and barrier locations. There exists a small region of the state diagram which is qualified by both glassy and gel localization lengths in the dynamic free energy. A much larger (high volume fraction, and high attraction strength) region of phase space is characterized by short gel-like localization lengths, and long barrier locations. The region is called the attractive glass and represents a 2-step relaxation process whereby a particle first breaks attractive physical bonds, and then escapes its topological cage. The dynamic fragility of fluids are highly particle shape dependent. It increases with particle dimensionality and falls with aspect ratio for quasi 1- and 2- dimentional particles. An ultralocal limit analysis of the NLE theory predicts universalities in the behavior of relaxation times, and elastic moduli. The equlibrium phase diagram of chemically anisotropic Janus spheres and Janus rods are calculated employing a mean field Random Phase Approximation. The calculations for Janus rods are corroborated by the full liquid state Reference Interaction Site Model theory. The Janus particles consist of attractive and repulsive regions. Both rods and spheres display rich phase behavior. The phase diagrams of these systems display fluid, macrophase separated, attraction driven microphase separated, repulsion driven microphase separated and crystalline regimes. Macrophase separation is predicted in highly attractive low volume fraction systems. Attraction driven microphase separation is charaterized by long length scale divergences, where the ordering length scale determines the microphase ordered structures. The ordering length scale of repulsion driven microphase separation is determined by the repulsive range. At the high volume fractions, particles forgo the enthalpic considerations of attractions and repulsions to satisfy hard core constraints and maximize vibrational entropy. This results in site length scale ordering in rods, and the sphere length scale ordering in Janus spheres, i.e., crystallization. A change in the Janus balance of both rods and spheres results in quantitative changes in spinodal temperatures and the position of phase boundaries. However, a change in the block sequence of Janus rods causes qualitative changes in the type of microphase ordered state, and induces prominent features (such as the Lifshitz point) in the phase diagrams of these systems. A detailed study of the number of nearest neighbors in Janus rod systems reflect a deep connection between this local measure of structure, and the structure factor which represents the most global measure of order.

The interpersonal and mental health implications of the coherence of coming out narratives for a sample of gay men in committed romantic relationships

The coming out process has been conceptualized as a developmental imperative for those who will eventually accept their same-sex attractions. It is widely accepted that homophobia, heterosexism, and homonegativity are cultural realities that may complicate this developmental process for gay men. The current study views coming out as an extra-developmental life task that is at best a stressful event, and at worst traumatic when coming out results in the rupture of salient relationships with parents, siblings, and/or close friends. To date, the minority stress model (Meyer, 1995; 2003) has been utilized as an organizing framework for how to empirically examine external stressors and mental health disparities for lesbians, gay men, and bisexual individuals in the United States. The current study builds on this literature by focusing on the influence of how gay men make sense of and represent the coming out process in a semi-structured interview, more specifically, by examining the legacy of the coming out process on indicators of wellness. In a two-part process, this study first employs the framework well articulated in the adult attachment literature of coherence of narratives to explore both variation and implications of the coming out experience for a sample of gay men (n = 60) in romantic relationships (n = 30). In particular, this study employed constructs identified in the adult attachment literature, namely Preoccupied and Dismissing current state of mind, to code a Coming Out Interview (COI). In the present study current state of mind refers to the degree of coherent discourse produced about coming out experiences as relayed during the COI. Multilevel analyses tested the extent to which these COI dimensions, as revealed through an analysis of coming out narratives in the COI, were associated with relationship quality, including self-reported satisfaction and observed emotional tone in a standard laboratory interaction task and self-reported symptoms of psychopathology. In addition, multilevel analyses also assessed the Acceptance by primary relationship figures at the time of disclosure, as well as the degree of Outness at the time of the study. Results revealed that participant’s narratives on the COI varied with regard to Preoccupied and Dismissing current state of mind, suggesting that the AAI coding system provides a viable organizing framework for extracting meaning from coming out narratives as related to attachment relevant constructs. Multilevel modeling revealed construct validity of the attachment dimensions assessed via the COI; attachment (i.e., Preoccupied and Dismissing current state of mind) as assessed via the Adult Attachment Interview (AAI) was significantly correlated with the corresponding COI variables. These finding suggest both methodological and conceptual convergence between these two measures. However, with one exception, COI Preoccupied and Dismissing current state of mind did not predict relationship outcomes or self-reported internalizing and externalizing symptoms. However, further analyses revealed that the degree to which one is out to others moderated the relationship between COI Preoccupied and internalizing. Specifically, for those who were less out to others, there was a significant and positive relationship between Preoccupied current state of mind towards coming out and internalizing symptoms. In addition, the degree of perceived acceptance of sexual orientation by salient relationship figures at the time of disclosure emerged as a predictor of mental health. In particular, Acceptance was significantly negatively related to internalizing symptoms. Overall, the results offer preliminary support that gay men’s narratives do reflect variation as assessed by attachment dimensions and highlights the role of Acceptance by salient relationship figures at the time of disclosure. Still, for the most part, current state of mind towards coming out in this study was not associated with relationship quality and self-reported indicators of mental health. This finding may be a function of low statistical power given the modest sample size. However, the relationship between Preoccupied current state of mind and mental health (i.e., internalizing) appears to depend on degree of Outness. In addition, the response of primary relationships figures to coming out may be a relevant factor in shaping mental health outcomes for gay men. Limitations and suggestions for future research and clinical intervention are offered.