Polyad quantum numbers

Long progressions of feature states in the two Franck-Condon active vibrational modes (CC stretch and /rani-bend) contain information about wavepacket dynamics in a two dimensional configuration space. Each feature state actually corresponds to a polyad, which is specified by three approximately conserved vibrational quantum numbers (the polyad quantum numbers nslretch, "resonance, and /total, [ r, res,fl)> and every symmetry accessible polyad is initially illuminated by exactly one a priori known Franck-Condon bright state. 

The finer structure within each feature state corresponds to the dynamics of the Franck-Condon bright state within a four-dimensional state space. This dynamics in state space is controlled by the set of all known anharmonic resonances. The state space is four dimensional because, of the seven vibrational degrees of freedom of a linear four-atom molecule, three are described by approximately conserved constants of motion (the polyad quantum numbers) thus 7-3 = 4. 

What is a polyad A polyad is a subset of the zero-order states within a specifiable region of Evib (typically a few hundred reciprocal centimeters) that are strongly coupled by anharmonic resonances to each other and negligibly coupled to all other nearby zero-order states. If approximate constants of motion of the exact vibration-rotation Hamiltonian exist, then the exact H can be (approximately) block diagonalized. Each subblock of H corresponds to one polyad and is labeled by a set of polyad quantum numbers. For the C2H2S0 state, a procedure proposed by Kellman [9, 10] identifies the three polyad quantum numbers... 

The polyad model for acetylene is an example of a hybrid scheme, combining ball-and-spring motion in a two-dimensional configuration space [the two Franck-Condon active modes, the C-C stretch (Q2) and the tram-bend (Q4)] with abstract motion in a state space defined by the three approximate constants of motion (the polyad quantum numbers). This state space is four dimensional the three polyad quantum numbers reduce the accessible dimensionality of state space from the seven internal vibrational degrees of freedom of a linear four-atom molecule to 7 - 3 = 4. 

In the present contribution the interpretation of the energy-level structure of quasi-one-dimensional quantum dots of two and three electrons is reviewed in detail by examining the polyad structure of the energy levels and the symmetry of the spatial part of the Cl wave functions due to the Pauli principle. The interpretation based on the polyad quantum number is applied to the four electron case and is shown to be applicable to general multi-electron cases. The qualitative differences in the energy-level structure between quasi-one-dimensional and quasi-ta>o-dimensional quantum dots are briefly discussed by referring to differences in the structure of their internal space. 

Figure 1 Energy spectrum of the low-lying states of four electrons confined in a quasi-one-dimensional Gaussian potential with (D, a>z,a>xy) = (4.0, 0.1, 20.0) for different-size basis sets. Energy levels of different spin multiplicities are indicated by different colors (See the caption to Figure 2). The number in the round brackets specifies the total number of basis functions and the parameter v p specifies the extended polyad quantum number (See the text for details). (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this book.)...

The polyad quantum number is defined as the sum of the number of nodes of the one-electron orbitals in the leading configuration of the Cl wave function [19]. The name polyad originates from molecular vibrational spectroscopy, where such a quantum number is used to characterize a group of vibrational states for which the individual states cannot be assigned by a set of normal-mode quantum numbers due to a mixing of different vibrational modes [19]. In the present case of quasi-one-dimensional quantum dots, the polyad quantum number can be defined as the sum of the one-dimensional harmonic-oscillator quantum numbers for all electrons. 

When more than one anharmonic interaction term couples near-degenerate, zero-order levels, a simple vector orthogonalization technique can be used to generate a complete set of the dynamically important (i.e., approximately conserved) polyad quantum numbers (Fried and Ezra, 1987 Kellman, 1990). For example, in acetylene, HC = CH, where the ratios of normal mode frequencies u2 W3 W4 W5 are approximately 5 3 5 1 1, modes 1, 2, and 3 are stretching modes (respectively symmetric CH stretch, and CC stretch, and antisymmetric CH stretch), modes 4 and 5 are bending modes (trans-bend and cis-bend), each polyad is labeled by 3 polyad quantum numbers,... 

The 9 important anharmonic resonances destroy all of the 7 normal mode quantum numbers (iq, rq, v3, u4, I4, v3, I5), but three approximately conserved polyad quantum numbers remain,... 

The three polyad quantum numbers serve to block diagonalize the total vibrational H into individual, scaling-related polyads, Heff ([Astretch, AreKOnance],total) The coordinate space or state space dimensionality is reduced from 7 to (7 — 3) =... 

The v4l4v5l5) normal mode basis states form polyads (see Section 9.4.5), which are labeled by the approximately good polyad quantum numbers, N and... 

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