Amy S. Mullin

Bio: Amy S. Mullin is an academic researcher from University of Maryland, College Park. The author has contributed to research in topics: Excited state & Rotational energy. The author has an hindex of 28, co-authored 96 publications receiving 2366 citations. Previous affiliations of Amy S. Mullin include Columbia University & Joint Institute for Nuclear Research.

Gas-phase SN2 and E2 reactions of alkyl halides

Abstract: Rate coefficients have been measured for the gas-phase reactions of methyl, ethyl, n-propyl, isopropyl, tert-butyl, and neopentyl chlorides and bromides with the following set of nucleophiles, listed in order of decreasing basicity: HO − , CH 3 O − , F − , HO − (H 2 O), CF 3 CH 2 O − , H 2 NS − , C 2 F 5 CH 2 O − , HS − , and Cl − . For methyl chloride the reaction efficiency first falls significantly below unity with HO − (H 2 O) as the nucleophile and for methyl bromide with HS − as the nucleophile; in both cases the overall reaction exothermicity is about 30 kcal mol −1 . Earlier conclusions that these halides react slowly with stronger bases are shown to be in error. In the region where the rates are slow oxygen anions react with the alkyl chlorides and bromides by elimination while sulfur anions of the same basicity react by substitution. This difference is due to a slowing down of elimination with the sulfur bases; sulfur anions show no increased nucleophilicity as compared to oxy anions of the same basicity

The philosophy of childhood

Abstract: So many questions, such an imagination, endless speculation: the child seems to be a natural philosopher - until the ripe old age of eight or nine, when the spirit of inquiry mysteriously fades. What happened? Was it something we did - or didn't do? Was the child truly the philosophical being he once seemed? Gareth Matthews takes up these concerns in "The Philosophy of Childhood", an account of children's philosophical potential and of childhood as an area of philosophical inquiry. Seeking a philosophy that represents the range and depth of children's inquisitive minds, Matthews explores both how children think and how we, as adults, think about them. Adult preconceptions about the mental life of children tend to discourage a child's philosophical bent, Matthews suggests, and he probes the sources of these limiting assumptions: restrictive notions of maturation and conceptual development; possible lapses in episodic memory; and the experience of identity and growth as "successive selves", which separate us from our own childhoods. By exposing the underpinnings of our adult views of childhood, Matthews, a philosopher and long time advocate of children's rights, clears the way for recognizing the philosophy of childhood as a legitimate field of inquiry. He then conducts us through various influential models for understanding what it is to be a child, from the theory that individual development recapitulates the development of the human species to accounts of moral and cognitive development, including Piaget's revolutionary model. The metaphysics of playdough, the authenticity of children's art, the effects of divorce and intimations of mortality on a child - all have a place in Matthews's discussion of the philosophical nature of childhood. His book should prompt us to reconsider the distinctions we make about development and the competencies of mind, and what we lose by denying childhood its full philosophical breadth.

Molecular supercollisions: Evidence for large energy transfer in the collisional relaxation of highly vibrationally excited pyrazine by CO2

Abstract: The temperature dependence of the collisional quenching of highly vibrationally excited pyrazine by CO2 molecules has been investigated for the temperature range 243–364 K using high resolution time resolved diode laser spectroscopy. Particular emphasis is placed on vibration to rotation‐translation (V→R/T) energy transfer which leaves the CO2 vibrations unexcited and occurs predominantly through short‐range repulsive forces. Vibrationally hot pyrazine is prepared by 248 nm excimer laser pumping, followed by rapid radiationless transitions to the ground electronic state. For the range of experimental cell temperatures used here, the nascent rotational population distributions of the 0000 ground state of CO2 resulting from collisions with hot pyrazine were probed at short times following excitation of pyrazine by the excimer laser pulse. The CO2 translational recoil velocity was also measured for individual rotational levels of the 0000 state. In addition, temperature dependent rate constants and probabili...

The visible photoabsorption spectrum of Ar+3

Abstract: The photodissociation cross section of Ar+3 was measured at a number of wavelengths between 1064 and 320 nm. A single broad and featureless band was observed peaking near 520 nm with a width of ≈2600 cm−1 and a peak cross section of ≈10−16 cm2. Consideration of the electronic structure of Ar+3 indicates that the measured spectrum is equivalent to the photoabsorption spectrum. Two ionic products, Ar+ and Ar+2, were observed in the photodissociation of Ar+3, indicative of at least two exit pathways and suggestive of two electronic transitions.

Chemistry with ADF

Abstract: We present the theoretical and technical foundations of the Amsterdam Density Functional (ADF) program with a survey of the characteristics of the code (numerical integration, density fitting for the Coulomb potential, and STO basis functions). Recent developments enhance the efficiency of ADF (e.g., parallelization, near order-N scaling, QM/MM) and its functionality (e.g., NMR chemical shifts, COSMO solvent effects, ZORA relativistic method, excitation energies, frequency-dependent (hyper)polarizabilities, atomic VDD charges). In the Applications section we discuss the physical model of the electronic structure and the chemical bond, i.e., the Kohn–Sham molecular orbital (MO) theory, and illustrate the power of the Kohn–Sham MO model in conjunction with the ADF-typical fragment approach to quantitatively understand and predict chemical phenomena. We review the “Activation-strain TS interaction” (ATS) model of chemical reactivity as a conceptual framework for understanding how activation barriers of various types of (competing) reaction mechanisms arise and how they may be controlled, for example, in organic chemistry or homogeneous catalysis. Finally, we include a brief discussion of exemplary applications in the field of biochemistry (structure and bonding of DNA) and of time-dependent density functional theory (TDDFT) to indicate how this development further reinforces the ADF tools for the analysis of chemical phenomena. © 2001 John Wiley & Sons, Inc. J Comput Chem 22: 931–967, 2001

The New York Review of Books

Abstract: It comes as something ofa surprise to reflect that the New York Review ofBooks is now over twenty years old. Even people of my generation (that is, old enough to remember the revolutionary 196os but not young enough to have taken a very exciting part in them) think of the paper as eternally youthful. In fact, it has gone through years of relatively quiet life, yet, as always in a competitive journalistic market, it is the controversies that attract the interest of the reader and to which the history (especially an admittedly impressionistic survey that tries to include something of the intellectual context in which a journal has operated) must give some attention. Not all the attacks which the New York Review has attracted, both early in its career and more recently, are worth more than a brief summary. What do we now make, for example, of Richard Kostelanetz's forthright accusation that 'The New York Review was from its origins destined to publicize Random House's (and especially [Jason] Epstein's) books and writers'?1 Well, simply that, even if the statistics bear out the charge (and Kostelanetz provides some suggestive evidence to support it, at least with respect to some early issues), there is nothing surprising in a market economy about a publisher trying to push his books through the pages of a journal edited by his friends. True, the New York Review has not had room to review more than around fifteen books in each issue and there could be a bias in the selection of

The Woman in the Body: A Cultural Analysis of Reproduction

Abstract: The Woman in the Body: A Cultural Analysis of Reproduction by Emily Martin Beacon Press, 1987 Paperback, 276 pp $1195 Winner of the 1988 Eileen Basker Memorial Prize As anthropology at its best can do, this book exposes hidden cultural assumptions about the nature of reality Martin has produced a powerful study of the dialectic between medical metaphors for women's reproductive processes and women's own views of those processes She and her associates interviewed 165 white and black women, seeking a balance between the three life stages of puberty, childbearing, and menopause 43% of her interviewees were working-class; 57% middleclass Early on Martin came up against one of the greatest dangers of studying one's own society Hearing women discuss uterine contractions as separate from the self and labor as something one "went through," and reading the same in medical texts, she at first thought that her interviews had turned up views of the body that simply reflected actual scientific fact It took her some time to realize that such scientific views are not "fact" but culturally grounded statements of an underlying ideology To get at this ideology Martin studied medical texts for the "grammar" that scientific medicine uses to describe female bodies In this medical grammar, she finds industrial society writ small The female reproductive tract is a machine designed to produce a baby; accordingly, menstruation represents failed production, connoting both a productive system that has failed to produce and one that produces only useless waste Such metaphors, disturbing to a society whose existence depends upon continued production, lead to menstruation's description in medical texts in highly negative terms: The fall in blood progesterone and estrogen, which results from regression of the corpus luteum, deprives the highly developed endometrial lining of its hormonal support Disintegration starts The endometrial arteries dilate, resulting in hemorrhage through the weakened capillary walls; the menstrual flow consists of this blood mixed with endometrial debris (quoted on p 48) (Martin contrasts this with a description of male reproductive physiology which speaks of the "remarkable" cellular transformation from spermatid to mature sperm, its "amazing" nature and "sheer magnitude") Confronting the argument that the above is not value-laden but simply a factual description of menstruation, Martin examines medical descriptions of the analogous regular shedding and replacement of the lining of the stomach, finding in a number of texts no references to degeneration, but instead a stress on the periodic "renewal" of the stomach lining Concluding that writers can choose to depict what happens to the lining of stomachs and uteruses either negatively as breakdown and decay or positively as continual production and replenishment, Martin suggests an alternative medical description of menstruation: A drop in the formerly high levels of progesterone and estrogen creates the appropriate environment for reducing the excess layers of endometrial tissue Constriction of capillary blood vessels causes a lower level of oxygen and nutrients and paves the way for a vigorous production of menstrual fluids Such a description would far more accurately reflect women's own more positive assessments of the menstrual fluid as the desired product Viewing pregnancy as the sole purpose of female reproductive organs and despising menstruation as a "waste" ignores the reality that most women do not intend to get pregnant most of the time (and so are often joyful when menstruation begins), and conceals "the true unity women have [Menstruation is] the one thing we all share" (p 112) In spite of ambivalence about the "disgusting mess," most interviewees felt that menstruation defines them as women and insisted that they wouldn't want to give it up Teens spoke of the joy of getting their periods so they could be part of the in-group that shared the women's "special secret," of mothers and sisters greeting their first menstruation with "You're a woman now! …

Critique of Judgment

Abstract: A study of Kant’s Critique of Judgment (1790). Our topics will include Kant’s motivations for a critique of judgment; principles of ‘reflective’ and ‘determining’ judgment; theory of aesthetic judgment, including epistemology and metaphysics of the beautiful and sublime; theory of genius; teleology in the critical philosophy—including harmony of the cognitive faculties, organisms, scope and limits of mechanical explanation, physicoand ethico-theology; the relation of ethics, aesthetics and teleology. A basic familiarity with Kant’s theoretical philosophy is presupposed.