It has almost nothing to do with mountains. It has to do with global air flow, trade winds, Hadley cells, and the like. South America has mountains AND desert.
There is a permanent low pressure area over the equator. The Sun is generally most intense over the equator, and heats the Earth; the warm air rises and cools, dumping all it’s moisture. Thus, lush tropical rain forests.
The cold, dry air makes its way South, and sinks. As it sinks, it warms up. Now you have warm, dry air falling to Earth, ready to soak up moisture like a sponge, and that air makes contact with the Earth at about the 25-30S latitude: right through the heart of Australia. It also forms the Kalahari desert in Africa, and the Atacama in South America.
Note: Some of the rising equatorial air goes North and sinks at the 20-30N latitude, forming the Sahara, the desert regions of the South West United States, and others.
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