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DTA and ESR methods were applied for studying photostimulated changes in molecular anenic (y-As). It is shown that under the effect of illuminatiodirradiation the stability of y-As decreases, which is due to the formation of stable fmgmene of the polymeric phase (a-As). Using the principles of orbital symmetry conservation. it is shown rhat polymenzation takes place most favourably from a staggered 'face to face' configuration of As4 molecules. Photopolymerization may proceed without activation. As a result we get a formation of an intermediate molecular cluster Ass of 'chairlike' symmetry D2h.

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