By Stuart A. Rice

ISBN-10: 0470226889

ISBN-13: 9780470226889

ISBN-10: 0470371560

ISBN-13: 9780470371565

This sequence presents the chemical physics box with a discussion board for severe, authoritative reviews of advances in each sector of the self-discipline.

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Extra resources for Advances in Chemical Physics Volume 140

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Also, since only the leading term or terms in the small-t expansion have been retained above, the neglected terms must increasingly contribute as t increases and the above explicit results must become increasingly inapplicable. Hence these results hold for t in the < t < tlong . intermediate regime, tshort $ $ The matrix Lð^tÞ is called the transport matrix, and it satisfies Lð^tÞ ¼ E Lð^tÞT E ¼ LðÀ^tÞT ð55Þ This follows because, in the grouped representation, Qþ contains nonzero blocks only on the diagonal and is symmetric, and QÀ contains nonzero blocks only off the diagonal and is asymmetric.

In the expression for the second entropy 38 phil attard of the isolated system, Eq. (109), the isolated system first entropy, Sð1Þ ðxÞ, must be replaced by the total first entropy, Sð1Þ ðxÞ À x Á Xr . With this replacement and adding the stochastic second entropy, the total second entropy is ð2Þ Stotal ðÁ0 x; Ár x; xjXr ; tÞ ¼ 1 g ðxÞ : ½Á0 xŠ2 þ fðx; ^tÞ Á ½Á0 xŠ þ Sð1Þ ðxÞ À x Á Xr 2jtj 0 þ 12½Sð1Þ ðx00 Þ À Sð1Þ ðx0 Þ À Ár x Á Xr Š ð143Þ Setting the derivative with respect to Ár x to zero, one finds X00s ¼ Xr ð144Þ As in the linear case, in the steady state the subsystem force equals the reservoir force at the end of the transition.

B. Parity In addition to the coefficients for the nonlinear second entropy expansion defined earlier, Eqs. (83), (84), and (85) define  qSð2Þ ðx; x0 jtÞ F ðx; tÞ  0 qx0 x ¼x  q2 Sð2Þ ðx; x0 jtÞ y G ðx; tÞ  qx0 qx0 x0 ¼x y and  q2 Sð2Þ ðx0 ; xjtÞ G ðx; tÞ  qx0 qx  z ð89Þ ð90Þ ð91Þ x0 ¼x Under the parity operator, these behave as Eðx; tÞ ¼ EðEx; tÞ ¼ Eðx; ÀtÞ y y Fðx; tÞ ¼ EF ðEx; tÞ ¼ F ðx; ÀtÞ y y Gðx; tÞ ¼ E G ðEx; tÞE ¼ G ðx; ÀtÞ ð92Þ ð93Þ ð94Þ 29 the second law of nonequilibrium thermodynamics and Gz ðx; tÞ ¼ E Gz ðEx; tÞT E ¼ Gz ðx; ÀtÞT ð95Þ The matrices G and Gy are symmetric.

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Advances in Chemical Physics Volume 140 by Stuart A. Rice


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